Sterically crowded peri-substituted naphthalene phosphines and their P v derivatives

FULL PAPER

DOI: 10.1002/chem.201000454

Sterically Crowded peri-Substituted Naphthalene Phosphines and their P^V

Derivatives

Fergus R. Knight, Amy L. Fuller, Michael Bꢀhl, Alexandra M. Z. Slawin, and

J. Derek Woollins*^[a]

Abstract: Three sterically crowded

peri-substituted naphthalene phos-

analysed by naphthalene ring torsions,

peri-atom displacement, splay angle

magnitude, X···E interactions, aromatic

ring orientations and quasi-linear ar-

rangements. An increase in the conges-

tion of the peri region following the in-

troduction of heavy chalcogen atoms is

accompanied by a general increase in

naphthalene distortion. P···E distances

increase for molecules that contain

bulkier atoms at the peri positions and

also when larger chalcogen atoms are

phines, Nap

N

bound to phosphorus. The chalco

ACHTUNGTRENNUNGgen-

thalene-1,8-diyl; ER=SEt, SPh, SePh)

1–3, which contain phosphorus and

chalcogen functional groups at the peri

positions have been prepared. Each

phosphine reacts to form a complete

series of P^Vchalcogenides Nap[P(E’)-

ACHTUNGTRENNiUNG des adopt similar conformations that

À

contain a quasi-linear E···P C frag-

ment, except for 3O, which displays a

twist-axial-twist conformation resulting

À

in the formation of a linear O···Se C

alignment. Ab initio MO calculations

performed on 2O, 3O, 3S and 3Se

reveal Wiberg bond index values of

0.02 to 0.04, which indicates only minor

non-bonded interactions; however, cal-

culations on radical cations of 3O, 3S

and 3Se reveal increased values (0.14–

0.19).

ACHTUNGTRENNUNG(Ph₂)(ER)] (E’=O, S, Se). The novel

compounds were fully characterised by

using X-ray crystallography and multi-

nuclear NMR spectroscopy, IR spec-

troscopy and MS. X-ray data for 1, 2,

nO, nS, nSe (n=1–3) are compared.

Eleven molecular structures have been

Keywords: chalcogens

·

density

functional calculations · intramolec-

ular interactions · oxidation · peri-

substitution · X-ray diffraction

Introduction

stituents occupying the peri positions.^[3]Repulsive steric ef-

fects caused by the crowding of substituents can be over-

come by attractive weak or strong intramolecular interac-

tions, or by the deformation of the naphthalene skeleton

away from ideal.^[3,4]This gives rise to structurally distorted

compounds with unusual bonding and geometry.^[3]

X-ray structural data has played a crucial role when ana-

lysing the extent of steric strain and the amount of distor-

tion occurring in non-ideal naphthalenes and has helped to

elucidate attractive effects between peri atoms and verify

the existence of weak intra- and intermolecular interac-

tions.^[4]To quantify the extent of naphthalene distortion

taking place in a given molecule, the naphthalene geometry

is compared with that of ideal or un-substituted naphtha-

lene.^[2,5,6]

peri-Substituted naphthalenes incorporating large hetero-

ACHTUNGTRENNUNGatoms confined in close proximity with separations shorter

than the sum of the van der Waals (vdW) radii have re-

ceived great attention.^[1]Un-substituted (“ideal”) naphtha-

lene is known to be rigidly planar with unequal bond lengths

and bond angles.^[2]The peri-carbon atoms are separated by

a distance of 2.44 ꢀ,^[2]which is sufficient to accommodate

two hydrogen atoms, but it is reasonable to expect that

there will be considerable steric hindrance with larger sub-

[a] F. R. Knight, Dr. A. L. Fuller, Dr. M. Bꢁhl, Prof. A. M. Z. Slawin,

Prof. J. D. Woollins

School of Chemistry

Steric strain operating between crowded peri atoms can

also be relieved by coordination of the bidentate ligand to a

bridging metal centre, forming a stable ring complex (che-

late).^[7]Phosphines, being neutral two-electron donors, are

one of the most versatile ligands that can bind to late-transi-

tion metals.^[8]The complexes they form are important in or-

ganic synthesis and have been shown to act as active homog-

University of St Andrews

St Andrews, Fife

KY16 9ST (UK)

Fax : (+44)1334-463384

E-mail: jdw3@st-and.ac.uk

Supporting information for this article is available on the WWW

under http://dx.doi.org/10.1002/chem.201000454, and contains X-ray

crystallographic data for compounds 1, 2, nO, nS and nSe (n=1–3).

Chem. Eur. J. 2010, 16, 7617 – 7634

ꢂ 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

7617

A

Results and Discussion

development of a novel class of 1,8-bisphosphine bidentate

ligand that uses the rigid C₃naphthalene backbone and posi-

tions phosphino groups peri-substituted on the ring has re-

ceived great attention over the last 30 years.^[1c,10]

Compounds 1–3 and their chalcogeno derivatives were syn-

thesised and crystal structures were determined for 1, 2, nO,

nS and nSe (n=1–3). All derivatives were spectrally charac-

terised by multinuclear NMR and IR spectroscopy and mass

spectrometry and the homogeneity of the new compounds

was, where possible, confirmed by microanalysis. ³¹P and

⁷⁷Se NMR spectroscopy data for all compounds is displayed

in Table 1.

Extensive work has also been carried out on mixed donor

phosphorus–nitrogen compounds.^[11]A leading topic of cur-

rent research and one which has seen much controversy,

concerns the possible occurrence of intramolecular dative

bond formation leading to hypercoordination.^[11,12]Most of

the pertinent work in this field has been performed by using

8-dimethylaminonaphth-1-yl (DAN) compounds in which

the nitrogen atom can donate a pair of electrons in the for-

mation of a coordination bond with acceptor heteroatoms,

such as Si or P.^[13]Upon bond formation, the acceptor spe-

cies finds itself with a greater than normal co-ordination

number and is termed “hypercoordinate”.^[13]

Table 1. ³¹P and ⁷⁷Se NMR spectroscopic data (d [ppm], J [Hz]) for phos-

phines 1–3 and related chalcogeno derivatives.

1

1O

36

n/a

2O

37

n/a

3O

38

n/a

450

n/a

1S

52

n/a

2S

53

n/a

3S

51

n/a

449

19

1Se

42

À172

2Se

42

À341

722

3Se

41

À163

451

24

d_P

À5

n/a

2

À5

n/a

3

À13

n/a

440

391

n/a

d_Se

d_P

Unlike bis-phosphines and DAN–phosphorus compounds,

phosphorus–oxygen, phosphorus–sulfur and phosphorus–se-

lenium peri-substituted naphthalenes have received limited

attention in the literature. These exciting new phosphorus

d_Se

¹J

ACTHNUTRGNE(NUG P,Se)

d_P

d_Se

ligACHTUNGTRENNUNGands provide good models with which to study naphtha-

lene distortion, intramolecular interactions (including possi-

ble dative bonding and hypercoordination) and metal com-

plexation. The difference in the electronic properties be-

tween the donor atoms of the new (P,O), (P,S) and (P,Se)

systems means these compounds could also be of value as

hemi-labile ligands.^[14]

During our early studies of sterically crowded 1,8-disubsti-

tuted naphthalenes we investigated dichalcogenide ligands^[15]

and unusual phosphorus compounds.^[7,16]More recently we

reported the synthesis and structural study of mixed halo-

gen–chalcogen^[5]and chalcogen–chalcogen^[6]systems and the

preparation of a novel mixed-donor phosphorus–oxygen

ligand.^[17]A preliminary study of the coordination chemistry

of novel phosphorus–sulfur ligand 2 has also been present-

ed.^[18]

⁴J

ACHTUNGTRENNUNG

¹J

A

n/a

715

We recently reported the synthesis of a series of 1-halo-8-

(alkylchalcogeno)naphthalene derivatives (4–5) prepared

from the stepwise halogen–lithium exchange reactions of

analogous 1,8-dibromonaphthalene and 1,8-diiodonaphtha-

lene.^[5]These compounds are ideal intermediates in the

preparation of phosphorus–chalcogen peri-substituted sys-

tems 1–3. For the synthesis, the respective halogen–chalco-

gen compound was treated with a single equivalent of n-bu-

tyllithium in diethyl ether to afford the respective 1-lithio-8-

(phenylchalcogeno)naphthalene precursor. Treatment with a

single equivalent of chlorodiphenylphosphine under stan-

dard reactions conditions^[20]afforded the respective peri-sub-

stituted naphthalene phosphines 1–3 (yields based on the

bromo and iodo starting material, respectively: 1 11 and

51%; 2 64 and 74%, 3 40 and 60%; Scheme 1).

Herein we report the synthesis and a comprehensive

structural study of (8-phenylsulfanylnaphth-1-yl)diphenyl-

phosphine 2,^[18]along with two analogous mixed phospho-

rus–chalcogen peri-substituted systems, (8-ethylsulfanyl-

naphth-1-yl)diphenylphosphine

1

and (8-phenylselanyl-

naphth-1-yl)diphenylphosphine 3.^[19]Compounds 1–3 react

to form complete series of mono-oxidised oxygen, sulfur

and selenium derivatives, and the synthesis and molecular

study of these nine compounds is also presented (Figure 1).

Scheme 1. The preparation of (8-alkylchalocgenonaphth-1-yl)diphenyl-

phosphines 1–3. Conditions: i) nBuLi (1 equiv), Et₂O, À788C, 1 h;

ii) ClPPh₂(1 equiv), Et₂O, À788C, 1 h.

Compounds 1–3 were characterised by elemental analysis,

IR spectroscopy, ¹H, ¹³C and ³¹P NMR spectroscopy and

mass spectrometry. Compound 3 was analysed by using

Figure 1. Sterically crowded peri-substituted naphthalene phosphines 1–3

and their phosphorus(V) oxygen, sulfur and selenium derivatives nO, nS,

nSe (n=1–3).

7618

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Chem. Eur. J. 2010, 16, 7617 – 7634

peri-Substituted Naphthalene Phosphines

FULL PAPER

⁷⁷Se NMR spectroscopy. Similar chemical shifts were ob-

served in the ³¹P NMR spectra of sulfur compounds 1 (d_P=

À5.24 ppm) and 2 (d_P=À5.30 ppm). The ³¹P and ⁷⁷Se NMR

X-ray investigations: Compound 3 is an oil at room temper-

ature, but suitable single crystals were obtained for all other

derivatives by diffusion of pentane into saturated solutions

of the individual compound in dichloromethane. The molec-

ular structures were analysed, although 2^[18]and 3O^[19]have

been previously reported. Compound 1 crystallises with two

nearly identical molecules in the asymmetric unit, all other

compounds contain one molecule in the asymmetric unit.

Selected interatomic distances, angles and torsion angles are

listed in Tables 2 and 3. Further crystallographic information

can be found in Tables 7, 8 and 9 and the Supporting Infor-

mation.

spectra for 3 (d_P=À12.94 ppm; d_Se=439.6 ppm; ⁴J

ACHTUNGTRNE(NUNG P,Se)=

391.0 Hz) are in accord with literature values (d_P=

À12.51 ppm; d_Se=446.2 ppm; ⁴J

(P,Se)=380.9 Hz;^[19]see

ACHTUNGTRENNUNG

Table 1).

Phosphines 1–3 react to form a series of three phospho-

ACHTUNGTRENNUNG

The molecular structures of 1 and 2 are shown in Fig-

ures 2 and 3, respectively. Overall, the degree of steric strain

operating between the peri atoms in SACTHNUTRGNEUNG(ethyl) derivative 1 is

Scheme 2. The preparation of the phosphorus(V) chalcogenide deriva-

tives of 1–3. Conditions: Toluene, 808C.

stoichiometric amounts of sulfur and selenium powder

under reflux selectively affords novel sulfides 1S, 2S, 3S and

selenides 1Se, 2Se, 3Se, respectively. Conversion of 1–3 to

the respective P^Vchalcogenide derivative was achieved in

1

100% yield in each case, as observed by H and ³¹P NMR

spectroscopy.

The P^Vchalcogenides were characterised by elemental

1

analysis, IR spectroscopy, H, ¹³C and ³¹P NMR spectroscopy

Figure 2. The crystal structure of (8-ethylsulfanylnaphth-1-yl)diphenyl-

phosphine 1 showing two independent molecules in the asymmetric unit.

and mass spectrometry. Compounds 1Se, 2Se, 3O, 3S and

3Se were analysed by using ⁷⁷Se NMR spectroscopy. Charac-

terisation data for 3O (d_P=37.99 ppm; d_Se=450.4 ppm)

were found to be in accord with the literature values (lit.:

d_P=37.47 ppm; d_Se=457.9 ppm).^[19]

A downfield shift was observed in the ³¹P{¹H} NMR spec-

tra of the four-coordinate phosphorus compounds compared

to the chemical shifts of the three-coordinate phosphines 1–

3. ³¹P{¹H} NMR spectra showed single peaks at comparable

shifts for the oxides (d_P=36.34 (1O), 37.01 (2O), 37.99 ppm

(3O)), sulfides (d_P=51.84 (1S), 52.52 (2S), 51.01 ppm

(3Se)) and selenides (d_P=41.92 (1Se), 42.46 (2Se),

4

40.50 ppm (3Se)). Expected ¹J and J values for phospho-

rus–selenium coupling were observed in the spectra of 3Se

Figure 3. The crystal structure of (8-phenylsulfanylnaphth-1-yl)diphenyl-

4

1

(¹J

G

N

T

phosphine 2.^[18]

ACHTUNGTRENNUNG

3S (Table 1).

notably reduced compared to the SACTHUNGETRNNU(G phenyl) analogue 2. The

Single peaks in the ⁷⁷Se NMR spectra of 1Se, 2Se and 3O

displacement of the peri atoms to opposite sides of the

mean naphthalene plane occurs to a slightly unequal degree

in the two independent molecules of 1 (À0.11 (0.05), 0.16 ꢀ

(À0.03 ꢀ)). In compound 2 (0.007, 0.13 ꢀ),^[18]the phospho-

rus atom lies virtually on the naphthyl plane. Positive splay

angles are observed for both compounds 1 (11.7 (11.48)) and

2 (14.1, 188), but there is a notable increase in the splay of

displayed no J

3S displayed a doublet at d=448.5 ppm with a small

⁴J

(Se,P) coupling value of 19.1 Hz. Two sharp doublets were

observed in the ⁷⁷Se NMR spectrum of 3Se (d=451.4 and

ACHTUNGTRENNUNG

(Se,P) coupling. The ⁷⁷Se NMR spectrum for

ACHTUNGTRENNUNG

1

4

À162.8 ppm), with J and J values for selenium–phosphorus

coupling of 715 and 24 Hz, respectively (Table 1).

Chem. Eur. J. 2010, 16, 7617 – 7634

ꢂ 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

www.chemeurj.org

7619

J. D. Woollins et al.

Table 2. Selected interatomic distances [ꢀ] and angles [8] for 1, 1O, 1S and 1Se.^[a]

The geometrical structures of

compounds 1 and 2 can be de-

scribed by the conformation

1

1O

1S

1Se

peri-Region distances and sub-vdW contacts in the peri region

P(1)···S(1)

2.9737(14) (2.9469(15))

0.6263 (0.6531)

83 (82)

1.838(4) (1.848(3))

3.1349(13)

0.4651

87

1.832(3)

1.772(3)

1.487(2)

3.033(2)

0.287

3.2083(14)

0.3917

89

1.837(3)

1.783(4)

1.9550(14)

3.2951(15)

0.305

3.2283(19) and arrangement of the naph-

Sr_vdWÀP···S^[b]

0.3717

thyl ring and ethyl/phenyl

groups relative to the two

C(ar)-P(1)-C(ar) planes and the

[b]

Sr_vdW[%]

90

1.843(5)

1.771(6)

À

P(1) C(1)

À

S(1) C(9)

1.779(4) (1.776(4))

C(ar)-S(1)-C(R) plane. This can

be categorised from torsion

P(1)=E(2)

–

2.1103(17)

3.43(1)

0.270

S(1)···E(2)

Sr_vdWÀS···E^[b]

angles

q and g, respectively

[b]

Sr_vdW[%]

91

92

93

(see Table 4). When q and g ap-

proach 908 the orientation is

denoted axial and when the

angles indicate a quasi-planar

arrangement (close to 1808),

they are termed equatorial.^[24]

When angle q is axial, the re-

Naphthalene bond lengths

À

C(1) C(2)

1.383(4) (1.373(5))

1.406(5) (1.416(5))

1.367(5) (1.355(5))

1.413(5) (1.413(5))

1.445(5) (1.438(5))

1.424(5) (1.416(6))

1.356(5) (1.338(6))

1.400(5) (1.410(6))

1.367(5) (1.379(5))

1.461(5) (1.438(5))

1.442(5) (1.466(5))

1.382(5)

1.387(5)

1.369(5)

1.418(5)

1.426(5)

1.411(5)

1.368(5)

1.386(6)

1.379(5)

1.439(5)

1.444(4)

1.384(5)

1.411(5)

1.360(5)

1.412(5)

1.430(5)

1.420(5)

1.365(6)

1.408(6)

1.377(5)

1.443(5)

1.438(5)

1.364(6)

1.408(8)

1.358(7)

1.417(6)

1.434(7)

1.401(7)

1.373(7)

1.397(8)

1.378(7)

1.443(6)

1.456(6)

À

C(2) C(3)

À

C(3) C(4)

À

C(4) C(5)

À

C(5) C(10)

À

C(5) C(6)

À

C(6) C(7)

À

C(7) C(8)

À

spective P C_Ph/S C_Rbond lies

perpendicular to the naphthyl

plane whereas an equatorial

conformation aligns the bond

on or close to the plane. Based

on the classification system pre-

sented by Nakanishi et al.,^[25]

axial conformations of angle q

correspond to a type -A struc-

ture and equatorial to type B.

The twist conformation is thus

type C.^[24,25]From the nomen-

clature reported by Nakanishi

et al.,^[25]compounds 1 and 2

can thus be described as type

BA-B and BA-C-c, respectively

(c denotes a cis orientation of

phenyl groups with respect to

À

C(8) C(9)

À

C(9) C(10)

À

C(10) C(1)

peri-Region bond angles

P(1)-C(1)-C(10)

C(1)-C(10)-C(9)

S(1)-C(9)-C(10)

S of bay angles

Splay angle^[c]

123.6(3) (122.4(3))

126.9(3) (126.0(3))

121.2(3) (123.0(3))

371.7 (371.4)

11.7 (11.4)

118.1(4) (118.9(4))

163.3(1) (160.6(1))

123.9(2)

126.5(3)

122.7(2)

373.1

13.1

118.2(3)

174.3(1)

124.5(2)

126.0(3)

121.4(2)

371.9

11.9

119.4(3)

175.4(1)

124.2(3)

127.2(4)

122.4(4)

373.8

13.8

118.7(5)

170.9(1)

C(4)-C(5)-C(6)

S(1)···P(1)-C(11)

Out-of-plane displacement

P(1)

S(1)

E(2)

Central naphthalene ring torsion angles

C(6)-C(5)-C(10)-C(1)

C(4)-C(5)-C(10)-C(9)

À0.11(1) (0.05(1))

0.16(1) (À0.03(1))

–

À0.566(4)

0.404(4)

À1.720(5)

À0.620(4)

0.744(4)

À2.019(5)

À0.599(7)

0.527(6)

À2.302(7)

À177.1(3) (179.8(4))

175.4(3)

175.0(3)

À168.4(3)

À171.0(3)

À173.7(6)

À175.3(6)

À176.5(3) (À177.2(4))

[a] Values in parentheses are for independent molecules. [b] vdW radii used for calculations: r_vdW(P) 1.80 ꢀ,

r_vdW(O) 1.52 ꢀ, r_vdW(S) 1.80 ꢀ, r_vdW(Se) 1.90.^[21][c] Splay angle: S of the three bay region anglesÀ360.

the

naphthyl

plane;

see

Figure 4).^[25]One quasi-linear

À

the P C and S C bonds in the SACTHNUTRGNE(UNG phenyl) derivative to alle-

viate the greater “peri-space crowding”.^[22]

The resulting geometry repels the P and S atoms to a

greater non-bonded interatomic distance of 3.0330(7) ꢀ in

2^[18]as compared with the

S

G

1

(2.9737(14) ꢀ (2.9469(15) ꢀ)). The peri gap in both cases is

still 16 to 18% shorter than the sum of their collective vdW

radii. The naphthalene units for both derivatives show only

minor deviations from planarity with maximum C-C-C-C

central naphthalene ring torsion angles of around 0 to 48.

Repulsive forces acting between the P and S atoms are ac-

Figure 4. The orientation of the phenyl and ethyl groups, the structure

type and the quasi-linear arrangements of 1 and 2.^[25]

À

companied by C C bond and C-C-C angle stretching in the

naphthalene scaffold. Bond lengths around C(10), closer to

the repulsive forces, are on average longer than those

around C(5) (average 1.45 and 1.42 ꢀ, respectively) and

C(1)-C(10)-C(9) bond angles splay to a mean 1278, wider

than the ideal geometry observed for C(4)-C(5)-C(6) (aver-

À

arrangement (S(1)···P(1) C(11)) with an angle of 174.58 is

observed in 2, whereas two linear arrangements

À

(S(1)···P(1) C(11) and P(1)···S(1) C(23)) with angles of

163.3 (160.6) and 161.18 (165.18), respectively, are observed

in 1.

The BA-C-c conformation in

ACHTUNGTREN(NGNU phenyl) groups and the (S)phenyl group on the same side

age 1198).^[2]S C (1.78–1.82 ꢀ) and P C (1.83–1.86 ꢀ) bond

lengths are within the usual ranges ((1.77Æ0.05), (1.84Æ

0.05) ꢀ, respectively)^[23]in both cases.

À

2 places one of the

P

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Chem. Eur. J. 2010, 16, 7617 – 7634

peri-Substituted Naphthalene Phosphines

FULL PAPER

Table 3. Selected interatomic distances [ꢀ] and angles [8] for 2, 2O, 2S, 2Se, 3O, 3S and 3Se.

2

2O

2S

2Se

3O

3S

3Se

peri-Region distances and sub-vdW contacts in peri region

P(1)···E(1)

3.0330(7)

0.567

84

3.1489(9)

0.4511

87

3.191(1)

0.409

89

3.190(1)

0.410

89

3.215(2)

0.485

89

3.2803(8)

0.4197

89

3.278(2)

0.422

89

Sr_vdWÀP···E^[a]

[a]

Sr_vdW[%]

À

P(1) C(1)

1.8548(19)

1.785(2)

–

1.835(3)

1.777(3)

1.492(2)

2.9612(17)

0.3588

89

1.837(3)

1.779(3)

1.9585(12)

3.3142(11)

0.2858

92

1.836(4)

1.782(4)

2.1181(11)

3.3974(10)

0.3026

92

1.826(5)

1.937(4)

1.476(4)

2.770(3)

0.65

1.837(3)

1.916(3)

1.9567(10)

3.3490(7)

0.351

1.825(6)

1.917(6)

2.1165(16)

3.4217(8)

0.3783

90

À

E(1) C(9)

P(1)=E(2)

E(1)···E(2)

Sr_vdWÀE···E

[a]

Sr_vdW[%]

81

91

Naphthalene bond lengths

À

C(1) C(2)

1.376(3)

1.404(3)

1.353(3)

1.415(3)

1.442(3)

1.420(3)

1.358(3)

1.399(3)

1.377(3)

1.437(3)

1.448(3)

1.380(5)

1.400(5)

1.365(5)

1.419(5)

1.430(5)

1.420(4)

1.355(5)

1.408(5)

1.376(4)

1.432(4)

1.443(4)

1.376(5)

1.414(5)

1.352(4)

1.422(5)

1.435(4)

1.419(4)

1.345(5)

1.401(5)

1.372(4)

1.433(4)

1.452(4)

1.385(5)

1.400(6)

1.363(6)

1.422(6)

1.431(6)

1.411(5)

1.356(7)

1.390(6)

1.372(5)

1.431(5)

1.454(5)

1.358(7)

1.423(7)

1.344(8)

1.410(8)

1.439(7)

1.425(8)

1.368(8)

1.398(7)

1.384(7)

1.409(6)

1.455(7)

1.385(4)

1.397(4)

1.354(4)

1.413(4)

1.429(4)

1.418(4)

1.347(4)

1.402(4)

1.389(4)

1.433(4)

1.450(3)

1.387(8)

1.417(9)

1.341(9)

1.416(9)

1.441(9)

1.419(8)

1.359(10)

1.387(10)

1.396(8)

1.437(9)

1.437(8)

À

C(2) C(3)

À

C(3) C(4)

À

C(4) C(5)

À

C(5) C(10)

À

C(5) C(6)

À

C(6) C(7)

À

C(7) C(8)

À

C(8) C(9)

À

C(9) C(10)

À

C(10) C(1)

peri-Region bond angles

P(1)-C(1)-C(10)

C(1)-C(10)-C(9)

E(1)-C(9)-C(10)

S of bay angles

Splay angle^[b]

124.07(13)

126.90(17)

123.11(13)

374.1

124.6(2)

126.2(3)

121.6(2)

372.4

124.2(2)

127.3(3)

122.2(2)

373.7

125.0(3)

126.6(3)

122.5(3)

374.1

123.6(3)

126.8(4)

125.1(3)

375.5

125.4(2)

126.7(2)

124.7(2)

376.8

126.5(4)

126.3(5)

124.5(4)

377.3

14.1

12.4

13.7

14.1

15.5

16.8

17.3

C(4)-C(5)-C(6)

118.60(18)

174.5(1)

–

119.6(3)

177.6(1)

145.4(1)

118.9(3)

174.0(1)

145.8(1)

119.0(4)

173.8(1)

149.1(1)

119.8(4)

167.9(1)

178.1(1)

118.6(2)

173.5(1)

145.0(1)

118.9(6)

172.9(1)

148.4(1)

À

E(1)···P(1) C(11)

À

E(2)···E(1) C(23)

Out-of-plane displacement

P(1)

E(1)

E(2)

0.007(1)

0.127(1)

–

0.6312(37)

À0.582(4)

1.6231(46)

0.633(4)

0.621(47)

À0.433(5)

2.3457(51)

À0.578(6)

0.450(6)

À1.458(8)

0.601(3)

À0.420(3)

2.179(4)

0.578(7)

À0.397(7)

2.314(8)

À0.451(4)

2.1977(43)

Central naphthalene ring torsion angles

C(6)-C(5)-C(10)-C(1)

C(4)-C(5)-C(10)-C(9)

178.49(16)

À179.5(2)

171.7(2)

170.3(2)

173.7(2)

173.4(2)

175.4(3)

173.1(3)

174.4(5)

170.5(5)

174.9(2)

173.6(2)

175.7(5)

175.1(5)

[a] vdW radii used for calculations: r_vdW(P) 1.80 ꢀ, r_vdW(O) 1.52 ꢀ, r_vdW(S) 1.80 ꢀ, r_vdW(Se) 1.90.^[21][b] Splay angle: S of the three bay region anglesÀ360.

Table 4. Torsion angles [8] categorising the naphthalene and ethyl/phenyl ring conformations in 1 and 2.^[a]

1

2

much higher than for known p–

p stacking (3.3–3.8 ꢀ),^[26]no p–

p interactions are observed.

Torsion angle

Conformation

Torsion angle

Conformation

Naphthalene ring conformations

C(10)-C(1)-P(1)-C(11)

C(10)-C(1)-P(1)-C(17)

C(10)-C(9)-S(1)-C(23)

q₁=167.8(1) (162.6(1))

q₂=À87.3(1) (À92.5(1))

q₃=168.3(1) (169.5(1))

Nap₁: equatorial

Nap₂: axial

Nap₃: equatorial

q₂=177.0(1)

q₂=78.6(1)

q₁=À129.2(1)

Nap₁: equatorial

Nap₂: axial

Nap₃: twist

All non-hydrogen atoms are

larger in size than a lone pair of

electrons, thus it is perhaps not

surprising that an increase in

steric strain is observed in chal-

cogenide derivatives nO, nS

and nSe (n=1–3) in which O, S

and Se atoms crowd the peri

space instead of the lone-pair in

phosphanyl compounds 1–3.

The heavy chalcogen atoms are

accommodated by a greater de-

Ethyl/phenyl group conformations

C(1)-P(1)-C(11)-C(12)

C(1)-P(1)-C(17)-C(18)

C(9)-S(1)-C(23)-C(24)

g₁=109.9(1) (96.1(1))

g₂=158.1(1) (158.5(1))

g₃=À174.4(1) (À174.7(1))

Ph₁: axial

Ph₂: equatorial

Et₁: equatorial

g₁=92.6(11)

g₂=17.8(1)

g₃=48.0(1)

Ph₁: axial

Ph₂: equatorial

Ph₃: twist

[a] Values in parentheses are for independent molecules. Definitions: Nap₁: naphthalene ring P(1) relative to

C₁-P₁-C₁₁; Nap₂: naphthalene ring P(1) relative to C₁-P₁-C₁₇; Nap₃: naphthalene ring S(1); Ph₁: P(1) phenyl

ring 11–16; Ph₂: P(1) phenyl ring 17–22; Ph₃: S(1) phenyl ring; Et₁: S(1) ethyl group; axial: perpendicular to

C(ar)-Z-C(R) plane; equatorial: coplanar with C(ar)-Z-C(R) plane; twist: intermediate between equatorial

and axial.

of the naphthyl plane and in close proximity (Figure 4).^[25]

The mixed axial-twist conformation of the two phenyl rings

(g₁=92.6(11)8; g₃=48.0(1)8) results in no significant overlap

and with a centroid–centroid distance of 4.32 ꢀ, which is

formation of the naphthalene geometry through an increase

in-plane and out-of-plane distortions and a significant twist-

ing of the naphthalene skeleton.

Chem. Eur. J. 2010, 16, 7617 – 7634

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www.chemeurj.org

7621

J. D. Woollins et al.

The degree of distortion is generally related to the size of

the atoms residing in the peri region. This is best observed

by comparing the magnitude of the peri-distance parameter

(Tables 2 and 3, Figure 5). In each set of chalcogenide deriv-

atives there is a marked lengthening of the peri gap as

larger atoms bind to phosphorus. The separation of the peri

atoms in selenium compounds 3O, 3S and 3Se is also nota-

bly larger compared with the derivatives of sulfur com-

pounds 1 and 2 (Figure 5). P···E distances (3.12–3.28 ꢀ) are

less than the respective sum of vdW radii for the two peri

atoms (3.60–3.70 ꢀ);^[21]in all cases this is between 87 and

90% of the vdW sum. For derivatives of 1 and 2, this is an

Figure 6. The least and most distorted naphthalene units for P^Vchalcoge-

nides 3Se and 1S, respectively.

eton away from planarity takes

place. Bond lengths around

C(10), closer to the repulsion,

are on average longer than

those around C(5) (average

1.44 and 1.42 ꢀ, respectively)

and

C(1)-C(10)-C(9)

bond

angles splay to a mean 1278

away from the ideal geometry

observed for C(4)-C(5)-C(6)

(average 1198). Central naph-

thalene ring C-C-C-C torsion

angles (4.3–11.68) illustrate the

extent and variation of twisting

occurring in the naphthalene

framework of the nine chalco-

genide derivatives (Figure 6),

which are notably less planar

compared with the backbones

of phosphines 1 and 2 (0.2–

À

3.58). S C (1.77–1.83 ꢀ), Se C

À

(1.92–1.94 ꢀ),

P C

(1.80–

1.84 ꢀ), P=O (1.48–1.49 ꢀ), P=

S

(1.96–1.97 ꢀ) and P=Se

Figure 5. Comparison of the peri distances of phosphines 1–3 and their P^Vchalcogenides.

(2.11–2.12 ꢀ) bond lengths are

within the usual ranges ((1.82Æ

0.05),

(1.93Æ0.05),

(1.84Æ

increase in the length of the peri distance by 4 to 8% upon

the exchange of the phosphorus lone pair for a chalcogen

atom. These short non-bonded peri distances indicate the

possible existence of weak intramolecular interactions.^[27]

The increased congestion of the peri space in the P^Vchal-

cogenide derivatives is accompanied by a significantly larger

displacement of the peri atoms to opposite sides of the

naphthalene best plane (0.40–0.74 ꢀ) compared with phos-

phines 1 and 2 (0.01–0.16 ꢀ; Figure 6). Considerable repul-

0.05), (1.49Æ0.05), (1.95Æ0.05), (2.09Æ0.05) ꢀ, respective-

ly)^[23]in all nine compounds. The P C lengths are slightly

À

shortened on oxidation from P^IIIin 1 and 2 to P^Vin the chal-

cogenide derivatives.

The molecular structures of 1O, 1S and 1Se are shown in

Figure 7. As expected, a general increase in the steric strain

is observed if larger atoms occupy the peri region. Non-co-

valent P···S peri distances (1O 3.1349(13) ꢀ; 1S

3.2083(14) ꢀ; 1Se 3.2283(19) ꢀ) are significantly longer

than the separation in 1 (2.9737(14) ꢀ (2.9469(15) ꢀ)), and

lengthen as the bulk of the atoms bound to phosphorus in-

creases. Nonetheless, all distances are shorter than the sum

of the vdW radii for phosphorus and sulfur by 0.37 to

0.47 ꢀ.

À

sion of the P C and E C bonds is also evident, with positive

splay angles (11.9–17.38) helping to alleviate the peri-space

crowding (Figure 5).^[22]The aforementioned distortions are

insufficient to overcome the steric strain that occurs in the

bay region and are thus supplemented by major deforma-

À

tions of the naphthalene geometry. C C bonds and C-C-C

angles are stretched and a buckling of the naphthalene skel-

The displacement of the peri atoms to opposite sides of

the best naphthalene plane is significantly greater in the

7622

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ꢂ 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

Chem. Eur. J. 2010, 16, 7617 – 7634

peri-Substituted Naphthalene Phosphines

FULL PAPER

Figure 7. The crystal structures of 1O (left), 1S (centre) and 1Se (right) showing the alignment of the SACHTUNRGTNE(NUG ethyl) groups and CH–p interactions.

chalcogenides (0.40–0.74 ꢀ) compared with 1 (0.03–0.16 ꢀ);

the greatest out-of-plane distortion was observed in 1S

(À0.62, 0.74 ꢀ). Positive splay angles for 1O (13.18) and

to the type A, B, C classification system presented by Naka-

nishi et al.,^[25]which can be used to describe the geometry of

the molecules (angle q: axial=type A, equatorial=type B,

twist=type C).^[24,25]The torsion angles q of the naphthalene

units in 1O, 1S and 1Se display the same equatorial/axial/

axial conformation with respect to the C(ar)-P(1)-C(ar) and

C(ar)-S(1)-C(R) planes. This arrangement corresponds to a

À

1Se (13.78) are comparable, which implies that the P C and

À

S C bonds are tilted apart to a similar extent to minimise

the steric repulsion acting in the peri region. Notably, the

splay angle of 1S (11.98) is smaller and similar to that of

phosphine 1 (11.78). The naphthalene units of 1O and 1Se

also show similar deviations from planarity, with maximum

C-C-C-C torsion angles in the range of 5 to 68. A major dis-

tortion of the naphthalene scaffold is observed in 1S with

the deviation from planarity being more pronounced and

larger than any of the chalcogenides reported here; the

maximum C-C-C-C torsion angle is 11.6 for C(6)-C(5)-

C(10)-C(1) (Figure 6).

BA-A-c type arrangement (FigACHTNUGRTNEUNG

ure 8);^[24,25]one P C_Phbond

À

and the S C_Etbond align perpendicular to and on the same

À

side of the naphthyl plane and the remaining P C_Phbond

adopts a position close to/on the plane.^[25]One quasi-linear

À

S···P C_Phinteraction is observed in each compound with

angles approaching linearity (174.3, 175.4, 170.98; Figure 8).

The BA-A-c conformation places one phenyl group and

the ethyl group attached to S(1) on the same side of the

naphthyl plane. The chalcogen bonded to P(1) is thus forced

to reside in the peri region and in close contact with S(1)

(Figure 7). In all cases the chalcogen atom lies below the

naphthyl plane, with, as expected, distances from the plane

increasing as the size of the atom increases (1O

À1.7200(51) ꢀ, 1S À2.019(5) ꢀ, 1Se À2.3022(69) ꢀ). The

non-covalent S(1)···E(2) separa-

As with the structures of compounds 1 and 2, the confor-

mation and arrangement of the naphthyl rings and ethyl and

phenyl groups for the P^Vchalcogenides can be categorised

relative to the two C(ar)-P(1)-C(ar) planes and the C(ar)-

S(1)-C(R) plane (from torsion angles q and g, respectively;

see Table 5). The torsion angle conformations can be related

tions in 1O (3.033(2) ꢀ), 1S

Table 5. Torsion angles [8] categorising the naphthyl ring and phenyl/ethyl group conformations in nO, nS and

nSe (n=1–3).^[a]

(3.2951(15) ꢀ)

and

1Se

(3.43(1) ꢀ) are shorter than the

sum of the vdW radii for the

two interacting atoms by 0.27

to 0.31 ꢀ and close enough to

suggest possible intramolecular

interactions.^[27]

Naphthalene ring conformations

Phenyl ring conformations

C(10)-C(1)-

P(1)-C(11)

C(10)-C(1)-

P(1)-C(17)

C(10)-C(9)-

E(1)-C(23)

C(1)-P(1)-

C(9)-E(1)-

C(23)-C(24)

C(11)-C(12)

C(17)-C(18)

1O q₁=À161.4(1); q₂=À89.3(1);

equatorial axial

1S q₁=À158.2(1); q₂=92.6(1);

equatorial axial

q₃=93.4(1);

axial

g₁=À105.7(1); g₂=À24.8(1);

g₃=79.1(1);

axial

equatorial

q₃=À89.1(1);

g₁=À98.7(1);

g₂=À160.7(1); g₃=179.4(1);

axial

equatorial

g₂=28.9(1);

equatorial

g₂=96.5(1);

axial

equatorial

A large number of reported

organosulfur compounds con-

tain conformations considerably

influenced by intramolecular sul-

1Se q₁=À164.9(1); q₂=85.3(1);

q₃=À90.9(1);

axial

q₃=95.3(1);

axial

q₃=90.6(1);

axial

q₃=92.0(1);

axial

q₃=134.5(1);

twist

q₃=91.7(1);

axial

q₃=93.6(1);

axial

g₁=74.2(1);

axial

g₃=À67.0(1);

equatorial

2O q₁=95.9(1);

axial

q₂=152.7(1);

equatorial

q₂=162.0(1);

equatorial

q₂=À88.3(1);

axial

g₁=154.9(1);

equatorial

g₁=160.9(1);

equatorial

g₁=À77.9(1);

axial

g₃=À170.0(1);

equatorial

g₃=179.5(1);

equatorial

2S q₁=À89.5(1);

g₂=À81.4(1);

ACHUTNGRENUNfG ur-nucleophile interacACHTUNGTRENNUNG

tions;^[27a]

axial

such as non-bonded S···O, S···N,

S···S and S···p interactions. In

these molecules the S···nucleo-

phile distance is significantly

shorter than the sum of the

sulfur and nucleophile vdW

2Se q₁=162.4(1);

equatorial

g₂=161.4(1);

equatorial

g₂=À7.2(1);

equatorial

g₂=164.2(1);

equatorial

g₂=À20.4(1);

equatorial

g₃=À178.6(1);

equatorial

3O q₁=146.5(1);

twist

q₂=À99.7(1);

g₁=À86.3(1);

g₃=À56.1(1);

twist

axial

3S q₁=162.4(1);

equatorial

q₂=À88.8(1);

axial

g₁=À79.4(1);

axial

g₁=102.5(1);

axial

g₃=À176.5(1);

equatorial

3Se q₁=162.9(1);

equatorial

q₂=À88.5(1);

g₃=À2.2(1);

equatorial

radii.^[27]

Although

the

axial

S(1)···E(2) distances 1O, 1S

and 1Se are in the range for in-

[a] Definitions: axial: perpendicular to C(ar)-Z-C(R) plane; equatorial: coplanar with C(ar)-Z-C(R) plane;

twist: intermediate between equatorial and axial.

Chem. Eur. J. 2010, 16, 7617 – 7634

ꢂ 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

www.chemeurj.org

7623

J. D. Woollins et al.

À

to envisage CH p interactions (C(23)···Cg

ACHTUNGTRENNUNG(17–23)

4.041(1) ꢀ, C(24)···Cg

AHCTUNGTRENNUNG

CH···p hydrogen-bond lengths are displayed in Table 6.

Table 6. Non-bonded (hydrogen bond) intramolecular ethyl–p interac-

tions [ꢀ] and angles [8] for chalcogenides 1O, 1S and 1Se.^[a]

À

D H···A

H···A

D···A

D H···A

À

C(23) H

(23a)···Cg

R

N

3.09(1)

3.59(1)

3.83(1)

2.90(1)

3.42(1)

3.16(1)

3.64(1)

4.04(1)

3.79(1)

3.58(1)

117.2(1)

85.4(1)

94.9(1)

151.5(1)

91.0(1)

106.8(1)

1O

À

C(23) H

C(24) H

C(23) H

ACHTUNGTRENNUNG

À

E

ACHTUNGTRENNUNG

1S

À

N

ACHTUNGTRENNUNG

À

(23a)···Cg

A

1Se

[a] Cg

À

C(23) H

ACHTUNGTRENNUNG

AHCTUNGTREG(NNUN 17–23) is the centroid of atoms C(17)–C(22). All CH bonds have

been refined to 0.99(1) A.

The molecular structures of 2O, 2S and 2Se are shown in

Figure 9. As expected, the P and S peri atoms are forced to

lie further apart in these chalcogenides than in phosphine 2

(3.0339(13) ꢀ), with longer intramolecular peri distances ac-

commodating the greater steric congestion of the peri

region. Oxide 2O (3.1489(9) ꢀ) and sulfide 2S

(3.1909(1) ꢀ) have lengths comparable to their SACHTUNGTRENNUNG(ethyl)

counterparts, whereas the separation of the peri atoms in

selenide 2Se (3.190(1) ꢀ) is shorter than expected and simi-

Figure 8. The orientation of the phenyl and ethyl groups, the structure

type and the quasi-linear arrangements of nO, nS and nSe (n=1–3).^[25]

tramolecular interaction, a rota-

À

tion around the C(1) P(1)

bond would bring the two inter-

acting moieties in closer contact

and produce shorter separations

in line with known non-bonded

interaction values.^[27]If an

S(1)···E(2) interaction takes

place it is likely to be weak and

not the fundamental influence

Figure 9. The crystal structures of phosphorus(V) chalcogenides 2O (left), 2S (centre) and 2Se (right).

on the geometry of the mole-

cules.

Although all three chalco

ACHTUNGTNERgNUNG en-

A

lar in size to the sulfide compounds. The displacement of

the peri-atoms to opposite sides of the least-squares naph-

thalene plane (0.43–0.63 ꢀ) is comparable throughout the

series of compounds and more pronounced than in phos-

phine 2 (0.01, 0.13 ꢀ). Corresponding splay angles of 13.7

and 14.18 imply that distortion of the bay area geometry is

also similar for 2S and 2Se, whereas a smaller but still posi-

tive splay angle of 12.48 is observed in 2O. Compound 2O

exhibits the largest amount of buckling within the naphtha-

lene unit, with central naphthalene ring C-C-C-C torsion

angles in the range of 8 to 108. The naphthalene scaffold

sees a smaller deviation from planarity in 2S and 2Se (ꢀ5–

78).

that the phenyl and ethyl moieties arranged cis to the naph-

thyl plane adopt different orientations and, therefore, inter-

act slightly differently.^[24,25]In 1O and 1Se the ethyl group

aligns with an axial conformation (g₃=79.1(1)8; g₃=

À

À67.0(1)8) in which the C(23) C(24) bond points directly

away from the closest phenyl ring (Figure 7). The

C(23)···centroid distance is small enough to suggest a possi-

ble CH p interaction for both 1O (C(23)···Cg

3.644(1) ꢀ) and 1Se (C(23)···Cg

These are weak non-covalent attractive “hydrogen-bond-

type” interactions between soft acids (CH) and soft bases (p

system), which have previously been shown to be important

in self-assembly and molecular recognition processes and in

determining conformations, selectivities of reactions and

crystal structures.^[28]The ethyl group in 1S aligns with an

À

G

ACHTUNGTRENNUNG

The S

ACHTUNGTRENNUNG

tures similar those of the SAHCTNUGTRENNNUG

thalene units adopting equatorial/axial/axial conformations

with respect to the C(ar)-P(1)-C(ar) and C(ar)-S(1)-C(R)

À

equatorial conformation (g₃=179.4(1)8), and the C(23)

C(24) bond lies parallel to the phenyl ring and close enough

planes (Figure 8).^[24,25]One quasi-linear S···P C_Phinteraction

À

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ꢂ 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

Chem. Eur. J. 2010, 16, 7617 – 7634

peri-Substituted Naphthalene Phosphines

FULL PAPER

with angles of 177.6, 174.0, and 173.88 is observed in each

compound (Figure 8). The cis orientation of phenyl groups

again forces the extra chalcogen atom to reside in the peri

region and in close contact with S(1); in all cases lying

above the naphthyl plane with distances from the plane in-

creasing as the size of the atom increases (2O 1.6231(46) ꢀ,

2S 2.1977(43) ꢀ, 2Se 2.3457(51) ꢀ; Figure 9). Non-bonded

interatomic S(1)···E(2) distances in 2O (2.9612(17) ꢀ), 2S

(3.3142(11) ꢀ) and 2Se (3.3974(10) ꢀ) are comparable to

naphthalene geometry is observed in 3O, 3S and 3Se than

in analogous sulfur compounds to alleviate the extra steric

strain. An increase in the distortion is also observed within

the group as the size of chalcogen bonded to P(1) increases.

Phosphorus and selenium functional groups lie in close

proximity to each other, with non-bonded peri distances in

3O (3.215(2) ꢀ), 3S (3.2803(8) ꢀ) and 3Se (3.278(2) ꢀ)

showing a general increase as the size of the chalcogen at

P(1) increases. The peri separation in selenide 3Se, like its

sulfur analogue 2Se, is shorter than expected and similar in

size to the separation in sulfide 3S. Unsurprisingly, the peri

those found for the SACTHNUTRGNEUNG(ethyl) derivatives and shorter than the

sum of the vdW radii for the two interacting atoms by 9 to

12%.^[21]This once again suggests that the non-bonded dis-

tance is close enough for possible weak intramolecular inter-

actions to occur.^[27]

Torsion angles (g) show that the phenyl rings arranged cis

to the naphthyl plane adopt equatorial conformations in all

three compounds and thus overlap in a slipped packing ar-

rangement.^[26]However, variations in the twist of the phenyl

groups are observed. A greater overlap of the rings is found

in 2S (g₁=160.9(1)8, g₃=179.5(1)8) and 2Se (g₂=161.4(1)8,

g₃=178.6(1)8), which adopt a parallel alignment similar to

the face-to-face offset arrangement (Figure 10).^[24,26]The

gaps observed for the SeACTHNUTRGNEU(GN phenyl) compounds are notably

larger than those for analogous chalcogenides that contain

sulfur functional groups at the C(9) position. Nonetheless,

all P···Se separations are shorter than the sum of the vdW

radii for phosphorus and selenium (3.70 ꢀ)^[21]by 0.42–

0.49 ꢀ.

A similar displacement of the peri atoms to either side of

the naphthalene least-squares plane is observed throughout

the series of Se

ACHTUNGTRENNUNG

comparable to the out-of-plane distortion for the SACHTUNGTRENNUNG

analogues (0.43–0.63 ꢀ). However, distortion within the

naphthyl plane is much more

pronounced in the selenium

compounds and increases signif-

icantly from oxide 3O to sele-

nide 3Se. Large and positive

splay angles of 15.5 (3O), 16.8

(3S) and 17.38 (3Se) illustrate a

major tilt of the peri bonds in

opposite directions to reduce

the greater steric repulsion

acting between the heavy atoms

in the bay region. The displace-

Figure 10. The crystal structures of 2O (left), 2S (centre) and 2Se (right) showing the orientation and overlap

of the phenyl rings.

ment of the phosphorus and se-

lenium substituents within and

out of the plane is accompanied

by a distortion of the usually

phenyl rings in 2O (g₁=154.9(1)8, g₃=170.0(1)8) twist in to-

wards one another and thus do not align parallel

(Figure 10). The distances between the two interacting cen-

planar and rigid C₁₀unit by a twist into a non-planar confor-

mation. The deformation of the naphthalene skeleton in se-

lenium compounds 3O, 3S and 3Se corresponds to the dis-

A

N

(23–28)) for all three compounds (2O

tortion occurring in the SACHTUGNTERN(UNG phenyl) chalcogenides 2O, 2S and

4.397(1) ꢀ, 2S 3.955(1) ꢀ, 2Se 3.995(1) ꢀ) is longer than

the range for typical centroid–centroid p stacking (3.3–

3.8 ꢀ),^[26]and no p–p stacking

2Se. Oxide 3O shows the greatest deviation from planarity

with central naphthalene ring torsion angles of 6 to 108,

is observed.^[26]

The molecular structures of

3O, 3S and 3Se are shown in

Figure 11. With the substitution

of the larger SeACHTUNGTRENNUNG(phenyl) moiety

at the C(9) peri position, con-

gestion of the peri region would

be expected to increase com-

pared with chalcogenides con-

taining the

SACHTUNGTRENNUNG(ethyl) and the

SACHTUNGTRENNUNG

Figure 11. The crystal structures of phosphorus(V) chalcogenides 3O (left), 3S (centre) and 3Se (right) show-

Greater deformation of the ing the difference between the CA-C and BA-A structures and the overlap of phenyl rings.

Chem. Eur. J. 2010, 16, 7617 – 7634

ꢂ 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

www.chemeurj.org

7625

J. D. Woollins et al.

whereas a smaller contortion of the scaffold is observed for

3S and 3Se (ꢀ4–68). In fact, the naphthalene unit of 3Se is

the most planar of the chalcogenides reported here

(Figure 6).

Compounds 3S and 3Se adopt the same BA-A-c type

Figure 12. Ab initio MO calculations were performed on models A and B

structure as the SACHTUNGTRENNUNG(ethyl) and SACHTUNGTERN(NUGN phenyl) chalcogenides, in

by Nakanishi et al.^[19]

which the conformation of the naphthalene unit is equatori-

al/axial/axial with respect to the C(ar)-P(1)-C(ar) and C(ar)-

S(1)-C(R) planes (Figures 8 and 13).^[24,25]One quasi-linear

À

Se···P C_Phinteraction exists in 3S and 3Se, with angles

MO calculations, the 3c–4e type interaction was reported to

À

173.5 and 172.98, respectively (Figure 8). Oxide 3O adopts a

similar but notably different structural arrangement to the

other chalcogenides reported here (Figure 11). Relative to

the C(ar)-P(1)-C(ar) and C(ar)-S(1)-C(R) planes, the naph-

thalene unit now assumes a twist/axial/twist arrangement

(q₁=146.5(1)8, q₂=À99.7(1)8, q₃=134.5(1)8) that corre-

induce a linear O···Se H alignment in the models, and the

À

structure of 3O with its linear O···Se C arrangement was,

therefore, reported to originate from the 3c–4e type interac-

[19]

À

tion of the linear O···Se C atoms.

To try and assess the possibility of direct P···Se and

E(2)···Se bonding interactions that would indicate an onset

of 3c–4e bonding, density functional theory computations

were performed for derivatives 2O, 3O, 3S and 3Se at the

B3LYP/6-31+G* level. For each compound, both linear-

sponds to a CA-C type structure (Figure 8).^[24,25]The P C_Ph

À

and Se C_Phbonds, which align along and perpendicular to

the naphthyl plane, respectively, in 3S and 3Se, are rotated

in 3O and lie at an intermediate angle (ꢀ458; Figure 11).

À

type arrangements (E(2)···E(1) C and E(1)···P C) were

evaluated (Figure 13). The Wiberg bond index (WBI),^[29]

which measures the covalent bond order, was calculated for

each linear arrangement, both for the structures found in

the solid and for the minima resulting from full geometry

optimisations in the gas phase. WBI values of 0.02 to 0.04

are obtained throughout, which indicates a very minor inter-

action between non-bonded atoms in these compounds. For

À

With this conformation, the linearity of the Se···P C_Phinter-

action in 3O is reduced (167.98); however, the twist confor-

mation of the SeACHTUNGTRENNUNG(phenyl) moiety promotes the formation of

a quasi-linear O···Se C_Pharrangement (178.18; Figure 8).^[24,25]

Both the BA-A and CA-C type structures position the

chalcogen atom bonded to P(1) in the peri-region and in

close contact with Se(1). E(2)···Se(1) non-bonded interatom-

ic distances in 3O (2.770(3) ꢀ), 3S (3.3490(7) ꢀ) and 3Se

(3.4217(8) ꢀ) increase across the series with separations

shorter than the sum of the vdW radii of the interacting

atoms in all cases.^[21]The O(1)···Se(1) contact in 3O is nota-

bly close, with a distance that is 19% shorter than the vdW

sum of oxygen and selenium. This distance is shorter than

expected when compared with the E(2)···E(1) distances ob-

served in the remaining chalcogenides reported herein,

which contain relatively longer distances (7–11% of the

vdW sum). These distances are short enough for the exis-

tence of non-bonded weak intramolecular interactions to

occur.^[27]

À

comparison, the fully covalent S S single bond in naphtho-

[1,8-cd]

R

3S and 3Se, the aromatic p stacking between the phenyl

groups at P and the chalcogen that is found in the solid is

lost upon optimisation (due to the missing dispersion inter-

action at that level), but this only slightly affects the com-

puted WBIs. When the equatorial Ph group on Se(1) in 1,8-

À

bis(phenylselanyl)naphthalene is replaced with Br, Se Se

distances as short as 2.516 ꢀ have been observed.^[30]

A

B3LYP computation for the latter molecule from the X-ray

structure affords a WBI of 0.55, which suggests a large

extent of 3c–4e bonding in this case. Judging from the re-

fined phosphorus–chalcogen and chalcogen–chalcogen dis-

tances, none of the species in the present study comes close

to such a bonding situation.

The parallel alignment of phenyl groups arranged cis to

the naphthyl plane in 3S and 3Se is confirmed by torsion

angles (g), which show that both rings adopt equatorial con-

formations (3S: g₂=164.2(1)8, g₃=À176.5(1)8; 3Se: g₂=

À20.4(1)8, g₃=À2.2(1)8). Although the rings adopt a paral-

lel displacement, the distance between the two interacting

Further calculations were performed on the radical cat-

ions of chalcogenides 2O, 3O, 3S and 3Se (Figure 13). Al-

though the WBI values for the phosphorus–chalcogen inter-

actions showed little change, the values for the E(2)···Se(1)

interaction in the radical cations of selenium compounds

3O, 3S, and 3Se increased to between 0.14 and 0.19, which

indicates a greater interaction compared with the neutral

species. This increase is a consequence of the nature of the

HOMO in the latter species, which consists essentially of p

orbitals on E(2) and Se(1) in an antibonding combination

(see Figure 14 for 3Se). Because MOs with the correspond-

ing bonding combination are lower in energy, removal of an

electron from the HOMO increases the net bond order be-

tween these atoms. No similar increase was observed for the

O(1)···S(1) interaction in 2O upon oxidation.

centroids (CgACHTUNGTRENNUNG(17–22)···CgHCATUNGTRENN(UGN 23–28)) is longer than the range

for typical centroid–centroid p interactions (3.3–3.8 ꢀ)^[26]for

both 3S (4.034(1) ꢀ) and 3Se (4.075(1) ꢀ), so no p–p stack-

ing is envisaged (Figure 11).

Compound 3 and its oxide 3O were previously reported

by Nakanishi et al. while they were studying non-bonded

lone-pair interactions in peri-substituted naphthalenes.^[19]

Quantum-chemical calculations performed on optimised

structures of models A and B (Figure 12) were used to re-

produce the structure around P and Se in 3O and to investi-

gate the effect of lone-pair orbitals in the non-bonded P···Se

interaction on the structure of the molecule. Based on their

7626

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ꢂ 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

Chem. Eur. J. 2010, 16, 7617 – 7634

peri-Substituted Naphthalene Phosphines

FULL PAPER

Figure 13. DFT calculations performed on chalcogenides 2O, 3O, 3S and 3Se and their radical cations (B3LYP/6-31+G* level).

techniques.^[31]Judging from the computed IP values, the

four chalogenides 2O, 3O, 3S and 3Se, could exhibit similar

electrochemical reactivity to naphtho[1,8-cd][1,2]dithiole

A

ACHTUNGTRENNUNG

and may be able to form charge transfer compounds.

Conclusion

Phosphorus–chalcogen naphthalenes 1–3 have been pre-

pared by using standard halogen–lithium exchange reactions

of 1-halo-8-(alkylchalcogeno)naphthalene derivatives,^[5]fol-

lowed by treatment with dichlorodiphenylphosphine. Com-

pounds 1–3 react to form a complete series of P^Vchalco

ACHTUNGTRENNUNG

AHCTUNGTRENNUNG

of an extra chalcogen atom in the peri region and by infer-

ence a greater deformation of the naphthalene geometry.

The presence of quasi-linear three-body fragments in the

À

chalcogenides (O···Se C_Ph/E···P C_Ph: 171–1788) accompa-

nied by O···Se and E···P distances shorter than the sum of

the vdW radii suggests attractive 3–4e interactions could be

operating. To try and assess the possibility of direct O···Se/

E···P bonding interactions that would indicate an onset of

3c–4e bonding in the chalcogenides, density functional

theory computations were performed for derivatives 2O,

3O, 3S and 3Se. Judging from the WBI^[29]values of 0.02 to

0.04, none of the species in the present study comes close to

such a bonding situation and instead steric affects dominate

the overall geometry of the molecules.

Figure 14. Selected MOs of the neutral and radical cation species of 3Se

(B3LYP level) showing bonding (bottom) and antibonding (top) combi-

nations of p orbitals on the Se atoms.

For each of the radical cations, the adiabatic and vertical

ionisation potentials were calculated, and the obtained

values of 6.84–6.20 and 7.05–6.70 eV, respectively

(Figure 13), are comparable to those of the known com-

pound naphtho

vertical IP values of 7.82 and 8.03 eV, respectively, comput-

ed at the same level. From previous unpublished work from

[1,8-cd]

E

We have recently reported a preliminary study of the co-

ordination chemistry of the novel phosphorus–sulfur ligand

2^[18]to show the potential of these ligands towards specific

metal coordination. The difference in electronic properties

between donor atoms (P,S) and (P,Se) gives these com-

pounds added value as hemilabile ligands^[14]and the pres-

the Woollins group it was shown that naphthoACTHNUTRGENUG[N 1,8-cd]-

ACHTUNGTRENNUNG[1,2]dithiole can undergo one-electron oxidation and forms

crystals of [C₁₀H₆S₂]⁺[BF₄]^Àusing electrocrystallisation

Chem. Eur. J. 2010, 16, 7617 – 7634

ꢂ 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

www.chemeurj.org

7627

J. D. Woollins et al.

tion was filtered under nitrogen and the solvent removed in vacuo (0.2 g,

ence of the extra chalcogen atom in the chalcogenides adds

the potential to form extended seven-membered chelate

complexes upon coordination with transition metals.^[32]

52%). The product was identified by using ¹H and ³¹P NMR spectrosco-

py.

(8-Ethylsulfanylnaphth-1-yl)diphenylphosphine oxide (Nap

ACHTUNGTRENNUNG[O:PPh₂]-

AHCTUNGTERG[NNUN SEt]; 1O): (8-Ethylsulfanylnaphth-1-yl)diphenylphosphine 3 readily oxi-

dised in contact with the atmosphere to give (8-ethylsulfanylnaphth-1-yl)-

diphenylphosphine oxide 16 as a white solid with 100% conversion, as

monitored by ³¹P NMR spectroscopy. Colourless crystals were obtained

by diffusion of pentane into a saturated solution of the product in di-

chloromethane. ¹H NMR (270 MHz, CDCl₃, 258C, TMS): d=7.92 (d, ³J-

Experimental Section

All experiments were carried out under an oxygen- and moisture-free ni-

trogen atmosphere by using standard Schlenk techniques and glassware.

Reagents were obtained from commercial sources and used as received.

Dry solvents were collected from a MBraun solvent system. 1-Halo-8-

(phenylchalcogeno)naphthalene derivatives^[5]were prepared from 1,8-di-

bromonaphthalene 11^[33]and 1,8-diiodonaphthalene 12.^[34]Elemental

analyses were performed by the University of St Andrews School of

Chemistry Microanalysis Service. IR spectra were recorded as KBr discs

in the range of 4000–300 cm^À1on a Perkin–Elmer System 2000 Fourier

AHCTUNGTRENNUNG

3

nap 6-H, 2ꢃPPh₂3–5-H), 7.28–7.22 (m, 1H; nap 3-H), 2.32 (q, J

7.4 Hz, 2H; SCH₂), 0.65 ppm (t, ³J

(H,H)=7.4 Hz, 3H; SCH₂CH₃);

¹³C NMR (67.9 MHz, CDCl₃, 258C, TMS): d=138.7 (d, J

(C,P)=12.5 Hz),

137.7 (s), 134.4 (d, J(C,P)=3.1 Hz), 131.3 (d, J(C,P)=9.3 Hz), 130.7 (d, J-

(C,P)=2.1 Hz), 128.4 (d, J(C,P)=12.4 Hz), 126.5 (s), 124.1 (d, J(C,P)=

ACHTUNGTRENNUNG(H,H)=

AHCTUNGTRENNUNG

A

ACHTUNGTRENNUNG

A

R

ACHTUNGTRENNUNG

14.6 Hz), 33.9 (s; CH₂), 13.5 ppm (s; CH₃); ³¹P NMR (109.4 MHz, CDCl₃,

258C, H₃PO₄): d=36.34 ppm; IR (KBr disk): n˜_max=3406 w, 3050 w, 2924

w, 2360 vs, 2341 vs, 1815 w, 1765 w, 1726 w, 1710 w, 1961 w, 1658 s, 1641 s,

1592 vs, 1548 s, 1536 s, 1482 s, 1438 vs, 1316 s, 1187 vs, 1112 s, 1096 s, 994

s, 885 s, 818 vs, 761 vs, 730 s, 715 w, 690 s, 562 vs, 539 vs, 524 s, 507 vs, 434

s, 403 w, 389 w, 363 cm^À1w; MS (ES⁺): m/z (%): 411.00 (100) [M+Na]⁺;

elemental analysis calcd (%) for C₂₄H₂₁POS: C 74.2, H 5.5; found: C

74.5, H 6.1.

1

transform spectrometer. H and ¹³C NMR spectra were recorded by using

a Jeol GSX 270 MHz spectrometer with d(H) and d(C) referenced to ex-

ternal tetramethylsilane. ³¹P and ⁷⁷Se NMR spectra were recorded by

using a Jeol GSX 270 MHz spectrometer with d(P) and d(Se) referenced

to external phosphoric acid and dimethylselenide, respectively. Assign-

ments of ¹³C and ¹H NMR spectra were made with the help of H–H

COSY and HSQC experiments. All measurements were performed at

258C. All values reported for NMR spectroscopy are in parts per million

(ppm). Coupling constants (J) are given in Hertz (Hz). Mass spectrome-

try was performed by the University of St Andrews Mass Spectrometry

Service. Electron impact mass spectrometry (EIMS) and chemical ionisa-

tion mass spectrometry (CIMS) were carried out by using a Micromass

GCT orthogonal acceleration time-of-flight mass spectrometer. Electro-

spray mass spectrometry (ESMS) was carried out by using a Micromass

LCT orthogonal accelerator time-of-flight mass spectrometer.

(8-Ethylsulfanylnaphth-1-yl)diphenylphosphine sulfide (Nap

[SEt]; 1S): Powdered sulfur (9 mg, 0.27 mmol) was added in small batch-

es to solution of (8-ethylsulfanylnaphth-1-yl)diphenylphosphine

ACHTUNGTRENNUNG[S:PPh₂]-

AHCTUNGTRENNUNG

a

3

(0.10 g, 0.27 mmol) in toluene (10 mL) at 08C. The mixture was stirred

for 30 min at 08C and then for 2 h at ambient temperature. The resulting

cloudy solution was filtered, the solvent was removed in vacuo and the

remaining oil was vigorously stirred with hexane (10 mL) overnight,

which resulted in a thick suspension. The yellow solid was collected by

filtration and the product was obtained as colourless crystals by diffusion

of pentane into a saturated solution of the solid in dichloromethane

(8-Ethylsulfanylnaphth-1-yl)diphenylphosphine (NapACTHNURGTENNUG[PPh₂]ACHTUNGTRNE[NUGN SEt]; 1)

Synthesis of 1 from 4Br: A solution of n-butyllithium (2.5m) in hexane

(0.5 mL, 1.1 mmol) was added dropwise to a freshly prepared solution of

1-bromo-8-(ethylsulfanyl)naphthalene (0.3 g, 1.1 mmol) in diethyl ether

(10 mL) at À10–08C (salted ice bath). The bright mixture was stirred for

2 h at this temperature, after which chlorodiphenylphosphine (0.24 g,

0.2 mL, 1.1 mmol) was added slowly, initially colouring the reaction mix-

ture a bright yellow that became pale yellow once the addition was com-

plete. Stirring was continued for a further 2 h at À10–08C, then the mix-

ture was allowed to warm to RT. The solvent was removed in vacuo and

hexane (40 mL) was added to precipitate out unwanted salts. The solu-

tion was filtered under nitrogen and the solvent removed in vacuo, then

the obtained yellow solid was recrystallised from toluene to give the title

product as colourless crystals (0.2 g, 40%). ¹H NMR (270 MHz, CDCl₃,

258C, TMS): d=7.82–7.63 (m, 5H; nap 4,5,7-H, 2ꢃPPh₂4-H), 7.39–7.30

(m, 2H; nap 3,6-H), 7.28–7.10 (m, 9H; nap 2-H, 2ꢃPPh₂2,3,5,6-H), 2.64

1

(0.02 g, 72%). H NMR (270 MHz, CDCl₃, 258C, TMS): d=7.98–7.89 (m,

2H; nap 4,5-H), 7.89–7.65 (m, 5H; nap 7-H, 2ꢃPPh₂2,6-H), 7.54–7.33

(m, 8H; nap 3,6-H, 2ꢃPPh₂3–5-H), 7.32–7.21 (m, 1H; nap 2-H), 2.18–

2.04 (m, 2H; SCH₂), 0.54 ppm (t, ³J

ACHTUNGTRENNUNG

A

R

ACHTUNGTRENNUNG

A

ACHTUNGTRENNUNG

J

N

ACHTUNGTRENNUNG

14.5 Hz), 35.2 (s; CH₂), 13.2 ppm (s; CH₃); ³¹P NMR (109.4 MHz, CDCl₃,

258C, H₃PO₄): d=51.84 ppm; IR (KBr disk): n˜_max=3048 w, 2957 s, 2923

vs, 2851 s, 1987 w, 1962 w, 1896 w, 1820 w, 1737 w, 1666 w, 1585 w, 1476 w,

1433 s, 1370 w, 1320 w, 1260 s, 1183 w, 1092 s, 1019 w, 991 w, 968 w, 920 w,

880 w, 849 w, 820 vs, 801 vs, 765 s, 746 s, 718 s, 690 s, 645 s, 609 w, 576 w,

546 w, 512 w, 490 w, 442 w, 407 cm^À1s ; MS (EI⁺): m/z (%): 374.98 (28)

[MÀEt]⁺, 342.99 (100) [MÀSEt]⁺, 188.96 (63) [MÀSPPh₂]⁺; elemental

analysis calcd (%) for C₂₄H₂₁PS₂: C 71.3, H 5.2; found: C 70.1, H 5.7.

(q, ³J

SCH₂CH₃); ¹³C NMR (67.9 MHz, CDCl₃, 258C, TMS): d=137.0 (s), 136.0

(s), 134.1 (d, J(C,P)=19.7 Hz), 130.8 (s), 130.0 (s), 128.6 (s), 128.4 (d, J-

(C,P)=7.2 Hz), 125.6 (d, (C,P)=5.8 Hz), 125.5 (s), 35.2 (s; CH₂),

ACHTUNGTRENNUNG ACHTUNTGREN(NUGN H,H)=7.4 Hz, 3H;

(H,H)=7.4 Hz, 2H; SCH₂), 0.91 ppm (t, ³J

ACHTUNGTRENNUNG

N

J

A

(8-Ethylsulfanylnaphth-1-yl)diphenylphosphine selenide (Nap

ACHTUNGTRENNUNG

13.3 ppm (s; CH₃); ³¹P NMR (109.4 MHz, CDCl₃, 258C, H₃PO₄): d=

À5.26 ppm; IR (KBr disk): n˜_max=3430 br, 3054 s, 2919 s, 2227 s, 1587 s,

1480 s, 1434 vs, 1308 s, 1261 s, 1185 s, 1096 vs, 1021 s, 997 s, 910 s, 820 s,

725 vs, 690 vs, 528 vs, 321 s, 294 cm^À1s; MS (ES⁺): m/z (%): 411.18 (100)

[M+K]⁺; elemental analysis calcd (%) for C₂₄H₂₁PS: C 74.2, H 5.5;

found: C 74.5, H 6.1.

G

1.5 mmol) and Se (0.12 g, 1.5 mmol) were heated under reflux in toluene

(10 mL) for 2 h. The resulting cloudy solution was filtered, the solvent

was removed in vacuo and the remaining oil was vigorously stirred with

hexane (10 mL) overnight, which resulted in a thick suspension. The

yellow solid was collected by filtration and the product was obtained as

colourless crystals by diffusion of pentane into a saturated solution of the

solid in dichloromethane (0.18 g, 65%). ¹H NMR (270 MHz, CDCl₃,

258C, TMS): d=7.84–7.82 (m, 2H; nap 4,5-H), 7.81–7.60 (m, 5H; nap 7-

H, 2ꢃPPh₂2,6-H), 7.42–7.40 (m, 1H; nap 6-H), 7.40–7.19 (m, 8H; nap

Synthesis of 1 from 4I: A solution of n-butyllithium (2.5m) in hexane

(0.4 mL, 1.0 mmol) was added dropwise to a freshly prepared solution of

1-iodo-8-ethylsulfanylnaphthalene (0.3 g, 1.0 mmol) in diethyl ether

(10 mL) at À10–08C (salted ice bath). The bright mixture was stirred for

2 h at this temperature, after which chlorodiphenylphosphine (0.23 g,

0.2 mL, 1.0 mmol) was added slowly, initially colouring the reaction mix-

ture a bright yellow that became pale yellow once the addition was com-

plete. Stirring was continued for a further 2 h at À10–08C, then the mix-

ture was allowed to warm to RT. The solvent was removed in vacuo and

hexane (40 mL) was added to precipitate out unwanted salts. The solu-

2,3-H, 2ꢃPPh₂3–5-H), 2.09–1.92 (m, 2H; SCH₂), 0.48 ppm (t, ³J

7.4 Hz, 3H; SCH₂CH₃); ¹³C NMR (67.9 MHz, CDCl₃, 258C, TMS): d=

138.3 (s), 137.5 (d, J(C,P)=10.4 Hz), 134.1 (d, J(C,P)=3.1 Hz), 133.4–

131.4 (brm), 130.6 (d, J(C,P)=2.0 Hz), 130.4 (s), 128.4 (d, J(C,P)=

12.4 Hz), 126.8 (s), 124.0 (d, J(C,P)=13.5 Hz), 35.9 (s; CH₂), 13.8 ppm (s;

CH₃); ³¹P NMR (109.4 MHz, CDCl₃, 258C, H₃PO₄): d=41.92 ppm;

ACHTUNGTRENNUNG(H,H)=

G

ACHTUNGTRENNUNG

U

ACHTUNGTRENNUNG

AHCTUNGTRENNUNG

7628

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Chem. Eur. J. 2010, 16, 7617 – 7634

peri-Substituted Naphthalene Phosphines

FULL PAPER

⁷⁷Se NMR (51.5 MHz, CDCl₃, 258C, PhSeSePh): d=À172.3 ppm; IR

(KBr disk): n˜_max=3047 w, 2952 w, 2922 s, 2851 w, 2360 vs, 2336 vs, 1475 w,

1435 s, 1318 w, 1247 w, 1180 w, 1096 s, 1088 s, 1023 w, 994 w, 973 w, 917 w,

880 w, 820 s, 764 s, 746 s, 690 vs, 615 w, 587 s, 565 s, 533 s, 508 s, 489 w,

442 w, 409 cm^À1w; MS (EI⁺): m/z (%): 343.07 (100) [MÀSe]⁺, 188.99

(15) [MÀSePPh₂]⁺; elemental analysis calcd (%) for C₂₄H₂₁PSSe: C 63.9,

H 4.7; found: C 63.4, H 4.7.

(32) [MÀSPh]⁺; elemental analysis calcd (%) for C₂₈H₂₁PSO: C 77.0, H

4.9; found: C 77.7, H 5.0.

(8-Phenylsulfanylnaphth-1-yl)diphenylphosphine sulfide (Nap

ACHTUNGTRENNUNG[S:PPh₂]-

AHCTUNGERTG[NNUN SPh]; 2S): Powdered sulfur (18.2 mg, 0.569 mmol) was added in small

batches to a solution of (8-phenylsulfanylnaphth-1-yl)diphenylphosphine

19 (0.239 g, 0.569 mmol) in toluene (10 mL) at 08C. The mixture was

stirred for 30 min at 08C and then for another 2 h at ambient tempera-

ture. The resulting cloudy solution was filtered, the solvent was removed

in vacuo and the remaining oil was vigorously stirred with hexane

(10 mL) overnight, which resulted in a thick suspension. The yellow solid

was collected by filtration and the product was obtained as colourless

crystal by diffusion of pentane into a saturated solution of the solid in di-

chloromethane (0.1 g, 44%). ¹H NMR (270 MHz, CDCl₃, 258C, TMS):

d=7.99–7.88 (m, 3H; nap 4,5,7-H), 7.54–7.48 (m, 1H; nap 6-H), 7.32–

7.10 (m, 12H; nap 2,3-H, 2 ꢃPPh₂2–6-H), 6.81–6.69 (m, 3H; SPh 3–5-

H), 5.93–5.87 ppm (m, 2H; SPh 2,6-H); ¹³C NMR (67.9 MHz, CDCl₃,

(8-Phenylsulfanylnaphth-1-yl)diphenylphosphine (NapACTHNURGTENNUG[PPh₂]ACHTUNGTRNE[NUGN SPh]; 2)

Synthesis of 2 from 5Br: A solution of n-butyllithium (2.5m) in hexane

(1.3 mL, 3.2 mmol) was added dropwise to a freshly prepared solution of

1-bromo-8-(phenylsulfanyl)naphthalene (1.02 g, 3.2 mmol) in diethyl

ether (30 mL) at À10–08C (salted ice bath). The bright mixture was

stirred for 2 h at this temperature, after which chlorodiphenylphosphine

(0.71 g, 0.6 mL, 3.2 mmol) was added slowly. The mixture was stirred for

a further 2 h at À10–08C, then allowed to warm to RT. The solvent was

removed in vacuo and hexane (40 mL) was added to precipitate out un-

wanted salts. The solution was filtered under nitrogen and the solvent re-

moved in vacuo to give a crude yellow solid that was recrystallised from

hexane to give the product as colourless crystals (0.9 g, 64%). ¹H NMR

(270 MHz, CDCl₃, 258C, TMS): d=7.93–7.81 (m, 2H; nap 4,5-H), 7.71

258C, TMS): d=140.7 (s), 137.7 (d, J

N

ACHTUNGTRENNUNG(C,P)=

3.1 Hz), 131.8 (s), 130.5 (s), 128.3 (d, JACHTUNGTRENNNUG

(s),125.3 (s), 124.4 (s), 124.2 ppm (s); ³¹P NMR (109.4 MHz, CDCl₃,

258C, H₃PO₄): d=52.52 ppm; IR (KBr disk): n˜_max=3446 br, 3062 w, 1966

w, 1847 w, 1579 s, 1543 w, 1473 s, 1430 s, 1381 w, 1357 w, 1321 s, 1302 s,

1272 w, 1199 w, 1177 s, 1150 s, 1089 s, 1022 w, 989 s, 916 w, 882 w, 824 s,

766 vs, 736 vs, 687 s, 642 vs, 611 s, 547 s, 578 w, 547 s, 523 s, 511 vs, 492 s,

468 s, 447 w, 407 cm^À1s; MS (ES⁺): m/z (%): 474.97 (100) [M+Na]⁺; ele-

mental analysis calcd (%) for C₂₈H₂₁PS₂: C 74.3, H 4.7; found: C 73.3, H

4.7.

(d, ³J

ACHTUNGTRENNUNG(H,H)=1.5 Hz, 1H; nap 2-H), 7.45–7.36 (m, 1H; nap 3-H), 7.36–

7.28 (m, 1H; nap 6-H), 7.26–7.13 (m, 11H; nap 2-H, 2ꢃPPh₂2–6-H),

7.09–6.97 (m, 3H; SPh 3–5-H), 6.77–6.70 ppm (m, 2H; SPh 2,6-H);

¹³C NMR (67.9 MHz, CDCl₃, 258C, TMS): d=140.0 (q), 139.8 (q), 137.6

(s), 137.0 (s), 135.6 (q), 134.1

(C,P)=9.4 Hz), 130.9 (s), 130.6 (s), 128.6 (s), 128.4 (d, J

128.1 (d, J(C,P)=3.1 Hz), 126.4 (q), 125.9 (s), 125.8 (s), 125.4 ppm (s);

ACHUTGTNRENNUG(d, JACHTUNGTRENNUNG

A

ACHTUNGTRENNUNG

(8-Phenylsulfanylnaphth-1-yl)diphenylphosphine

selenide

(Nap-

ACHTUNGTRENNUNG

A

ACHTUNGTRENNUNG

³¹P NMR (109.4 MHz, CDCl₃, 258C, H₃PO₄): d=À5.30 ppm; IR (KBr

disk): n˜_max=3050 s, 2963 s, 1949 w, 1884 w, 1828 w, 1579 s, 1544 s, 1472 s,

1432 vs, 1352 w, 1308 w, 1261 vs, 1197 s, 1092 vs, 1021 vs, 864 w, 817 vs,

801 vs, 767 vs, 740 vs, 691 vs, 592 w, 539 w, 499 s, 474 s, 424 w, 387 cm^À1s;

MS (ES^À): m/z (%): 459.20 (100) [M+K]⁺; elemental analysis calcd (%)

for C₂₈H₂₁PS: C 79.9, H 5.0; found: C 79.7, H 5.0.

19 (0.23 g, 0.55 mmol) and Se (0.047 g, 0.55 mmol) were heated under

reflux in toluene (10 mL) for 2 h. The resulting cloudy solution was fil-

tered, the solvent was removed in vacuo and the remaining oil was vig

ACHTUNGTRENNUNGor-

AHCTUNGERTGoNNUN usly stirred with hexane (10 mL) overnight, which resulted in a thick

suspension. The yellow solid was collected by filtration and the product

was obtained as yellow crystals by diffusion of pentane into a saturated

solution of the crude compound (0.2 g, 85%). ¹H NMR (270 MHz,

CDCl₃, 258C, TMS): d=8.00–7.91 (m, 3H; nap 4,5,7-H), 7.56–7.49 (m,

1H; nap 6-H), 7.30–7.10 (m, 12H; nap 2,3-H, 2ꢃPPh₂2–6-H), 6.77–6.67

(m, 3H; SPh 3–5-H), 5.86–5.81 ppm (m, 2H; SPh 2,6-H); ¹³C NMR

Synthesis of 2 from 5I: A solution of n-butyllithium (1.6m) in hexane

(1.9 mL, 3.0 mmol) was added dropwise to a freshly prepared solution of

1-iodo-8-(phenylsulfanyl)naphthalene (1.10 g, 3.0 mmol) in diethyl ether

(30 mL) at À10–08C (salted ice bath). The bright yellow mixture was

stirred for 2 h at this temperature, after which chlorodiphenylphosphine

(0.67 g, 0.5 mL, 3.0 mmol) was added slowly. The mixture was stirred for

a further 2 h at À10–08C, then allowed to warm to RT. The solvent was

removed in vacuo and hexane (40 mL) was added to precipitate out un-

wanted salts. The solution was filtered under nitrogen and the solvent re-

moved in vacuo to give a crude yellow solid that was recrystallised from

hexane (0.9 g, 74%). The product was identified by using ¹H and

³¹P NMR spectroscopy.

(67.9 MHz, CDCl₃, 258C, TMS): d=140.7 (s), 137.3 (d, J

134.2 (d, J(C,P)=3.2 Hz), 131.9 (s), 130.6 (d, J(C,P)=3.1 Hz), 128.3 (d, J-

(C,P)=12.4 Hz), 128.1 (s), 127.6 (s), 125.0 (s), 124.3 (s), 124.2 ppm (s);

³¹P NMR (109.4 MHz, CDCl₃, 258C, H₃PO₄): d=42.46 ppm (J

(P,Se)=

722.4 Hz); ⁷⁷Se NMR (51.5 MHz, CDCl₃, 258C, PhSeSePh): d=

(Se,P)=722.4 Hz); IR (KBr disk): n˜_max=2856 vs, 2395 w,

ACHTUNGTREN(NGNU C,P)=10.4 Hz),

A

ACHTUNGTRENNUNG

AHCTUNGTRENNUNG

ACHTUNGTRENNUNG

À341.0 ppm (d, J

ACHTUNGTRENNUNG

1718 w, 1646 s, 1542 w, 1461 vs, 1378 vs, 1308 w, 1181 w, 1120 w, 973 w,

886 w, 809 s, 722 s, 691 w, 616 w, 562 w, 539 w, 506 cm^À1w; MS (CI⁺): m/z

(%): 501.04 (4) [M+H]⁺, 421.12 (75) [MÀSe]⁺, 391.02 (12) [MÀSPh]⁺,

343.08 (100) [MÀSePh]⁺; elemental analysis calcd (%) for C₂₈H₂₁PSSe: C

67.3, H 4.2; found: C 65.9, H 4.4.

(8-Phenylsulfanylnaphth-1-yl)diphenylphosphine oxide (Nap

ACHTUNGTNER[NUNG O:PPh₂]-

ACHTUNGTRENNUNG

in contact with the atmosphere to give (8-phenylsulfanylnaphth-1-yl)di-

phenylphosphine oxide 21 as a white solid with 100% conversion, as

monitored by ³¹P NMR spectroscopy. Colourless crystals were obtained

by diffusion of pentane into a saturated solution of the obtained product

in dichloromethane. M.p./b.p. 50–528C; ¹H NMR (270 MHz, CDCl₃,

(8-Phenylselanylnaphth-1-yl)diphenylphosphine (NapACTHNURTGENNUG[PPh₂]ACHTUNGTRENN[UGN SePh]; 3)

Synthesis of 3 from 6Br: A solution of n-butyllithium (2.5m) in hexane

(1.1 mL, 2.8 mmol) was added dropwise to a freshly prepared solution of

1-bromo-8-(phenylselanyl)naphthalene (1.02 g, 2.8 mmol) in diethyl ether

(30 mL) at À10–08C (salted ice bath). The bright yellow mixture was

stirred for 2 h at this temperature, after which chlorodiphenylphosphine

(0.62 g, 0.5 mL, 2.8 mmol) was added slowly. The mixture was stirred for

a further 2 h at À10–08C, then allowed to warm to RT. The solvent was

removed in vacuo and hexane (40 mL) was added to precipitate out un-

wanted salts. The solution was filtered under nitrogen and the solvent re-

moved in vacuo to give the product as a yellow oil (0.5 g, 40%).

258C, TMS): d=7.97 (d, ³J

(H,H)=8.1 Hz, 1H; nap 5-H), 7.83 (dd, ³J

ACHTUNGTRENNUNG

N

ACHTUNGTRENNUNG

1.3 Hz, 1H; nap 7-H), 7.52–7.40 (m, 6H; nap 2,6-H, 2ꢃPPh₂2,6-H),

7.32–7.23 (m, 3H; nap 3-H, 2ꢃPPh₂4-H), 7.23–7.15 (m, 4H; 2ꢃPPh₂3,5-

H), 6.84–6.72 (m, 3H; SPh 3–5-H), 6.18–6.12 ppm (m, 2H; SPh 2,6-H);

¹³C NMR (67.9 MHz, CDCl₃, 258C, TMS): d=139.8 (s) 138.4 (d, J

ACHTUNGTRENNUNG

12.4 Hz), 134.2 (d, J

(C,P)=2.1 Hz), 128.2 (s), 128.1 (d, J

124.6 (s), 124.3 ppm (d, J

ACHTUNGTRENNUNG(C,P)=4.1 Hz), 131.2 (d, JCAHTUNGTRENNNUG

¹H NMR (270 MHz, CDCl₃, 258C, TMS): d=7.76 (dd, ³J

(H,H)=7.9 Hz,

G

ACHTUNGTRENNUNG

3

⁴J

7.52 (dd, J

A

E

AHCTUNGTRENNUNG

3

4

258C, H₃PO₄): d=37.01 ppm; IR (KBr disk): n˜_max=3393 w, 3051 w, 2360

vs, 2339 vs, 1954 w, 1868 w, 1843 w, 1769 w, 1716 w, 1699 w, 1651 w, 1581

w, 1557 w, 1539 w, 1519 w, 1507 w, 1475 s, 1435 vs, 1357 w, 1321 w, 1259 w,

1211 w, 1181 vs, 1153 s, 1111 s, 1097 s, 1067 s, 1024 w, 993 s, 930 w, 886 s,

827 vs, 770 s, 734 vs, 715 s, 689 vs, 632 w, 614 w, 587 w, 563 vs, 540 vs, 507

s, 455 s, 419 cm^À1w; MS (CI⁺): m/z (%): 437.12 (100) [M+H]⁺, 327.09

A

N

1H; nap 2-H), 7.30–7.05 ppm (m, 17H; nap 2,3-H, SPh 2–6-H, 2ꢃPPh₂

2–6-H); ¹³C NMR (67.9 MHz, CDCl₃, 258C, TMS): d=137.7 (s), 135.0

(s), 133.9 (d, J

ACHTUNGTREN(NUGN C,P)=5.2 Hz), 133.7 (s), 131.2 (s), 129.2 (s), 128.9 (s),

128.5 (d, JACTHNUGTENR(NUG C,P)=6.2 Hz), 128.3 (s), 127.4 (s), 126.1 (s), 125.6 ppm (s);

³¹P NMR (109.4 MHz, CDCl₃, 258C, H₃PO₄): d=À12.94 ppm (J

ACHTUNGTRENNUNG(P,Se)=

Chem. Eur. J. 2010, 16, 7617 – 7634

ꢂ 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

www.chemeurj.org

7629

J. D. Woollins et al.

386.2.0 Hz); ⁷⁷Se NMR (51.5 MHz, CDCl₃, 258C, PhSeSePh): d=

439.6 ppm (d, J(Se,P)=386.2.0 Hz); IR (KBr disk): n˜_max=3853 w, 3735 w,

(8-Phenylselanylnaphth-1-yl)diphenylphosphine selenide (Nap

ACHTUNGTRENNUNG

ACHTUNGTRENNUNG[Se:PPh₂]-

C

3673 w, 3649 w, 3628 w, 3049 w, 2911 w, 2851 w, 2360 vs, 2340 vs, 1734 w,

1699 w, 1651 w, 1558 w, 1541 w, 1474 w, 1433 s, 1310 w, 1259 w, 1193 w,

1153 w, 1088 w, 1021 w, 996 w, 971 w, 911 w, 815 s, 765 s, 739 s, 690 s, 669

s, 538 w, 504 w, 420 w, 397 w, 352 cm^À1w; MS (CI⁺): m/z (%): 469.06 (65)

[M+H]⁺, 391.02 (98) [M+H-Ph]⁺; elemental analysis calcd (%) for

(C₂₈H₂₁PSe)₄CDCl₃: C 68.2, H 4.4; found: C 68.4, H 4.6.

2.3 mmol) and Se (0.18 g, 2.3 mmol) were heated under reflux in toluene

(20 mL) for 2 h. The resulting cloudy solution was filtered, the solvent

was removed in vacuo and the remaining oil was vigorously stirred with

hexane (10 mL) overnight, which resulted in a thick suspension. The

yellow solid was collected by filtration and recrystallised by diffusion of

pentane into a saturated solution of the compound to give the product as

yellow crystals (0.8 g, 60%). ¹H NMR (270 MHz, CDCl₃, 258C, TMS):

Synthesis of 3 from 6I: A solution of n-butyllithium (2.5m) in hexane

(0.5 mL, 1.2 mmol) was added dropwise to a freshly prepared solution of

1-iodo-8-(phenylselanyl)naphthalene (0.50 g, 1.2 mmol) in diethyl ether

(30 mL) at À10–08C (salted ice bath). The bright yellow mixture was

stirred for 2 h at this temperature, after which chlorodiphenylphosphine

(0.27 g, 0.2 mL, 1.2 mmol) was added slowly. The mixture was stirred for

a further 2 h at À10–08C, then allowed to warm to RT. The solvent was

removed in vacuo and hexane (40 mL) was added to precipitate out un-

wanted salts. The solution was filtered under nitrogen and the solvent re-

moved in vacuo to give the product as a yellow oil (0.5 g, 89%); The

d=8.11 (dd, ³J(H,H)=7.2 Hz, ⁴J

ACTHNUTRGENNUG CAHTUNGTREN(NUGN H,H)=1.3 Hz, 1H; nap 5-H), 7.94–7.83

(m, 2H; nap 4,7-H), 7.43–7.14 (m, 13H; nap 2,3,6-H, 2ꢃPPh₂2–6-H),

6.88–6.74 (m, 3H; SPh 3–5-H), 6.27–6.19 ppm (m, 2H; SPh 2,6-H);

¹³C NMR (67.9 MHz, CDCl₃, 258C, TMS): d=141.4 (s), 137.4 (d, J-

A

ACHUTGTNRENNUG(C,P)=3.1 Hz), 131.2 (s), 130.8 (d, JACHTUNGTRENNUNG(C,P)=

AHCTUNGTRENNUNG

A

ACHTUNGTRENNUNG

⁷⁷Se NMR (51.5 MHz, CDCl₃, 258C, PhSeSePh): d=451.4 (d, ⁴J

ACHTUNGTRENNUNG

23.9 Hz), À162.8 ppm (d, ¹J

ACHTUNGTRENNUNG

1

product was identified by using H and ³¹P NMR spectroscopy.

vs, 1954 vs, 1918 vs, 1732 w, 1651 s, 1574 w, 1473 s, 1433 s, 1316 w, 1261 s,

1197 w, 1178 w, 1156 w, 1096 s, 1019 w, 995 w, 978 w, 905 w, 862 w, 824 s,

800 s, 774 w, 765 s, 748 s, 735 s, 686 s, 662 w, 615 w, 583 s, 557 s, 524 s, 505

s, 486 s, 458 s, 443 s, 413 cm^À1s; MS (EI⁺): m/z (%): 390.01 (5)

[MÀSePh]⁺, 311.10 (18) [MÀSe₂Ph]⁺, 236.94 (12) [MÀPh₃Se]⁺, 233.04

(100) [MÀSe₂Ph₂]⁺; elemental analysis calcd (%) for C₂₈H₂₁PSe₂: C 61.6,

H 3.9; found C 61.4, H 3.3.

(8-Phenylselanylnaphth-1-yl)diphenylphosphine oxide (Nap

ACHTUNGTRENNUNG

ACHTUNGTNER[NUNG O:PPh₂]-

oxidised in contact with the atmosphere to give (8-phenylselanylnaphth-

1-yl)diphenylphosphine oxide 35 as an orange solid with 100% conver-

sion, as monitored by ³¹P NMR spectroscopy. The obtained solid was re-

crystallised by diffusion of pentane into a saturated solution of the com-

pound to give the product as colourless crystals (42%). M.p./b.p. 50–

Crystal structure analyses: X-ray crystal structures for compounds 1 and

2 were collected at À180(1)8C by using a Rigaku MM007 high brilliance

RA generator (Mo_Karadiation, confocal optic) and Mercury CCD

system. At least a full hemisphere of data was collected by using w scans.

Intensities were corrected for Lorentz, polarisation and absorption. Data

for chalcogenide compounds nO, nS, nSe (n=1–3) were collected at

À148(1)8C by using a Rigaku ACTOR-SM Saturn 724 CCD area detec-

tor with confocal optic Mo_Karadiation (l=0.71073 ꢀ). The data were

corrected for Lorentz, polarisation and absorption. The data for the ana-

lysed complexes was collected and processed by using CrystalClear

(Rigaku).^[35]The structure was solved by direct methods^[36]and expanded

by using Fourier techniques.^[37]The non-hydrogen atoms were refined

anisotropically. Hydrogen atoms were refined by using the riding model.

All calculations were performed by using the CrystalStructure^[38]crystal-

lographic software package except for refinement, which was performed

by using SHELXL-97.^[39]Tables 7, 8 and 9 shows the details of the crys-

tallographic studies. CCDC-737039 (2), -776917 (1), -776918 (1O),

-776919 (1S), -776920 (1Se), -766921 (2O), -776922 (2S), -776923 (2Se),

-776924 (3O), -776925 (3S) and -776926 (3Se) contain the supplementary

crystallographic data for this paper. These data can be obtained free of

charge from The Cambridge Crystallographic Data Centre via

www.ccdc.cam.ac.uk/data_request/cif.

528C; ¹H NMR (270 MHz, CDCl₃, 258C, TMS): d=7.92 (d, ³J

8.2 Hz, 1H; nap 4-H), 7.88 (d, ³J

(H,H)=6.4 Hz, 1H; nap 5-H), 7.79 (d,

³J

(H,H)=8.1 Hz, 1H; nap 7-H), 7.57–7.48 (m, 4H; 2ꢃPPh₂2,6-H), 7.40–

ACHTUNGTRNE(NUNG H,H)=

AHCTUNGTRENNUNG

ACHTUNGTRENNUNG

7.32 (m, 3H; nap 2-H, 2ꢃPPh₂4-H), 7.30–7.21 (m, 6H; nap 3,6-H, 2ꢃ

PPh₂3,5-H), 6.97–6.90 (m, 1H; SPh 4-H), 6.90–6.81 (m, 2H; SPh 3,5-H),

ACHTUNGTRENNUNG

6.59 ppm (d, ³J(H,H)=7.2 Hz, 2H; SPh 2,6-H); ¹³C NMR (67.9 MHz,

CDCl₃, 258C, TMS): d=140.3 (s), 137.6 (q), 137.3 (q), 135.6 (q), 134.3

(s), 131.8 (d, J(C,P)=9.4 Hz), 131.1 (s), 130.3 (s), 128.6 (s), 128.4 (s),

128.2 (s), 127.1 (s), 126.1 (s), 123.8 ppm (d, J

(C,P)=15.5 Hz); ³¹P NMR

ACHTUNGTRENNUNG

AHCTUNGTRENNUNG

(109.4 MHz, CDCl₃, 258C, H₃PO₄): d=37.99 ppm; ⁷⁷Se NMR (51.5 MHz,

CDCl₃, 258C, PhSeSePh): d=450.4 ppm; IR (KBr disk): n˜_max=3423 br,

3053 s, 2924 w, 1960 w, 1893 w, 1809 w, 1589 w, 1472 s, 1436 vs, 1314 s,

1176 vs, 1115 vs, 1068 w, 1022 w, 997 w, 981 w, 923 w, 866 w, 821 s, 763 vs,

744 vs, 721 vs, 693 vs, 541 vs, 505 s, 469 w, 447 w, 426 cm^À1w; MS (ES⁺):

m/z (%): 507.02 (100) [M+Na]⁺; elemental analysis calcd (%) for

C₂₈H₂₁PSeO: C 69.4, H 4.4; found C 68.5, H 4.6.

(8-Phenylselanylnaphth-1-yl)diphenylphosphine sulfide (Nap

ACHTUNGTRENNUNG

ACHTUNGTNER[NUNG S:PPh₂]-

batches to a solution of (8-phenylselanylnaphth-1-yl)diphenylphosphine

32 (0.086 g, 0.21 mmol) in toluene (10 mL) at 08C. The mixture was

stirred for 30 min at 08C and then for 2 h at ambient temperature. The

resulting cloudy solution was filtered, the solvent was removed in vacuo

and the remaining oil was vigorously stirred with hexane (10 mL) over-

night, which resulted in a thick suspension. The yellow solid was collect-

ed by filtration and recrystallised by diffusion of pentane into a saturated

solution of the compound to give the product as colourless crystals

(0.05 g, 54%). M.p./b.p. 51–538C; ¹H NMR (270 MHz, CDCl₃, 258C,

Computational details: Geometries were fully optimised in the gas phase

at the B3LYP level^[40]by using Curtis and Binningꢄs 962(d) basis^[41]on Se

and 6–31+G(d) elsewhere, followed by calculation of the harmonic fre-

quencies to confirm the minimum character of each stationary point and

evaluation of WBI values,^[29]obtained in a natural bond orbital analy-

sis.^[42]The optimisations were started from the experimental structures

available from X-ray crystallography, for which the WBIs were also cal-

culated. Radical cations were re-optimised from the closed-shell minima

by using the unrestricted Kohn–Sham formalism (spin contamination was

negligible in all cases). The computations were performed by using the

Gaussian 03 suite of programs.^[43]

TMS): d=8.12 (dd, ³J(H,H)=7.1 Hz, ⁴J

ACHTUNGTRENNUNG ACHTUNGTRENN(UGN H,H)=1.4 Hz, 1H; nap 5-H),

8.00–7.88 (m, 2H; nap 4,7-H), 7.76–7.62 (m, 4H; 2ꢃPPh₂2,6-H), 7.48–

7.22 (m, 9H; nap 2,3,6-H, 2ꢃPPh₂3–5-H), 6.97–6.81 (m, 3H; SPh 3–5-

H), 6.43–6.35 ppm (m, 2H; SPh 2,6-H); ¹³C NMR (67.9 MHz, CDCl₃,

258C, TMS): d=141.2 (s), 137.9 (s), 134.3 (d, J

(C,P)=10.4 Hz), 131.1 (s), 130.8 (d, J(C,P)=2.0 Hz), 129.4 (s), 128.5 (d,

(C,P)=4.2 Hz), 128.3 (s), 127.3 (s), 125.6 (s), 123.9 ppm (s); ³¹P NMR

(109.4 MHz, CDCl₃, 258C, H₃PO₄): d=51.01 ppm; ⁷⁷Se NMR (51.5 MHz,

CDCl₃, 258C, PhSeSePh): d=448.5 ppm (d, J(Se,P)=19.1 Hz); IR (KBr

ACHTUNGERTN(NUNG C,P)=3.1 Hz), 132.0 (d, J-

A

ACHTUNGTRENNUNG

JACHTUNGTRENNUNG

AHCTUNGTRENNUNG

disk): n˜_max=2925 vs, 1871 vs, 1574 w, 1474 s, 1434 vs, 1375 w, 1317 w, 1260

s, 1192 w, 1177 w, 1095 s, 1064 w, 1021 s, 994 w, 936 s, 863 w, 797 vs, 769 s,

732 vs, 718 vs, 690 vs, 639 s, 539 s, 509 s, 454 w, 414 cm^À1w; MS (CI⁺):

m/z (%): 501.04 (3) [M+H]⁺, 419.10 (11) [MÀPh],⁺345.08 (100)

[MÀPh₂]⁺; elemental analysis calcd (%) for C₂₈H₂₁PSSe: C 67.2, H 4.2;

found C 66.7, H 3.9.

7630

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Chem. Eur. J. 2010, 16, 7617 – 7634

peri-Substituted Naphthalene Phosphines

FULL PAPER

Table 7. Crystallographic data for compounds 1, 1O, 1S and 1Se.

1

1O

1S

1Se

empirical formula

M_r

C₂₄H₂₁PS

372.44

C₂₄H₂₁OPS

388.46

C₂₄H₂₁PS₂

404.52

C₂₄H₂₁PSSe

451.42

T [8C]

À180(1)

À148(1)

colourless, prism

0.21ꢃ0.21ꢃ0.03

monoclinic

12.851(3)

10.384(3)

29.473(8)

–

91.689(8)

–

3931.5(18)

C2/c

À148(1)

crystal colour, habit

colourless, prism

0.06ꢃ0.06ꢃ0.03

triclinic

colourless, prism

0.21ꢃ0.18ꢃ0.15

monoclinic

11.652(2)

9.6047(18)

18.293(3)

–

colourless, prism

0.12ꢃ0.09ꢃ0.06

monoclinic

13.622(3)

9.3562(18)

17.224(4)

–

crystal size [mm³]

crystal system

a [ꢀ]

8.6734(17)

13.165(3)

17.525(4)

102.307(6)

96.444(6)

93.395(4)

1935.7(7)

b [ꢀ]

c [ꢀ]

a [8]

b [8]

92.268(5)

–

2045.6(6)

P2₁/c

112.028(4)

–

2034.9(8)

P2₁/n

g [8]

V [ꢀ³]

¯

space group

Z

P1

4

8

4

1_calcd[gcm^À3

]

1.278

784

1.312

1632

1.313

848

1.473

920

F

A

m

G

]

0.254

12531

0.0595

0.5879/1.000

6626

2.57

10443

0.044

0.946/0.992

3418

3044 (246)

13.89

0.0677

0.0844

0.2324

1.183

–

0.75

À0.84

3.446

12018

0.06

0.928/0.950

3571

3334 (246)

14.52

0.0658

0.0735

0.1767

1.274

20.33

11654

0.075

0.779/0.885

3570

3162 (246)

14.51

0.069

0.0808

0.1172

1.209

no. of reflns measured

R_int

min./max. transmissions

independent reflns

observed reflns (no. variables)

refln/parameter ratio

R₁(I>2.00s(I))

R (all reflns)

wR₂(all reflns)

GOF

3809 (470)

14.1

0.0614

0.1131

0.1245

0.952

–

0.382

À0.332

flack parameter

–

0.46

À0.42

–

0.49

À0.51

max. peak in final diff. map [eꢀ^À3

]

min. peak in final diff. map [eꢀ^À3

Table 8. Crystallographic data for compounds 2, 2O, 2S and 2Se.

2

2O

2S

2Se

empirical formula

M_r

T [8C]

C₂₈H₂₁PS

420.48

C₂₉H₂₃OPSCl₂

521.44

C₂₈H₂₁S₂P

452.57

C₂₈H₂₁PSSe

499.47

À148(1)

yellow, block

0.15ꢃ0.12ꢃ0.12

monoclinic

9.432(4)

17.849(6)

13.701(4)

–

À180(1)

colourless, platelet

0.10ꢃ0.10ꢃ0.10

monoclinic

11.1461(12)

8.8914(10)

21.587(2)

–

À148(1)

colourless, platelet

0.18ꢃ0.12ꢃ0.06

monoclinic

9.3241(13)

17.769(2)

13.7930(19)

–

crystal colour, habit

colourless, prism

0.09ꢃ0.09ꢃ0.09

triclinic

crystal size [mm³]

crystal system

a [ꢀ]

9.2265(17)

11.6406(16)

13.239(3)

b [ꢀ]

c [ꢀ]

a [8]

b [8]

90.837(4)

–

2139.1(4)

P2₁/c

98.54(2)

97.328(3)

–

2266.6(5)

P2₁/n

96.511(7)

–

2291.8(13)

P2₁/n

g [8]

112.23(2)8

1240.7(5)

V [ꢀ³]

¯

space group

Z

P1

4

2

4

1_calcd[gcm^À3

]

1.306

880

1.396

540

1.326

944

1.447

1016

F

A

m

N

]

0.239

13424

0.0325

0.8678/1.000

3774

3348 (272)

13.88

0.0408

0.0462

0.1049

1.042

–

0.906

À0.314

4.313

12814

0.041

0.961/0.962

4275

3896 (308)

13.88

0.0508

0.061

0.1469

1.203

–

3.191

12358

0.054

0.943/0.981

3948

3521 (281)

14.05

0.0582

0.0694

0.123

1.201

–

0.29

À0.36

18.131

12375

0.04

0.757/0.804

4012

3694 (281)

14.28

0.0427

0.0504

0.1537

1.231

–

0.56

no. of reflns measured

R_int

min./max. transmissions

independent reflns

observed reflns (no. variables)

refln/parameter ratio

R₁(I>2.00s(I))

R (all reflns)

wR₂(all reflns)

GOF

flack parameter

max. peak in final diff. map [eꢀ^À3

]

0.51

À0.51

min. peak in final diff. map [eꢀ^À3

À0.53

Chem. Eur. J. 2010, 16, 7617 – 7634

ꢂ 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

www.chemeurj.org

7631

J. D. Woollins et al.

Table 9. Crystallographic data for compounds 3O, 3S and 3Se.

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108 , 1057.

3O

3S

3Se

empirical formula

M_r

C₂₈H₂₁PSeO

483.41

C₂₈H₂₁PSeS

499.47

C₂₈H₂₁PSe₂

546.37

T [8C]

À148(1)

colourless,

block

À148(1)

[3] V. Balasubramaniyan, Chem. Rev. 1966 , 66 , 567.

crystal colour, habit colourless,

chunk

yellow, prism

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crystal size [mm³]

crystal system

a [ꢀ]

0.30ꢃ0.15ꢃ0.12 0.15ꢃ0.15ꢃ0.15 0.18ꢃ0.15ꢃ0.09

monoclinic

10.1430(16)

10.6578(17)

10.6907(19)

–

monoclinic

9.3748(15)

17.820(3)

13.847(2)

–

monoclinic

9.4797(12)

17.844(2)

13.7175(16)

–

b [ꢀ]

c [ꢀ]

a [8]

b [8]

100.935(4)

–

1134.7(3)

P2₁

97.820(5)

–

2291.7(6)

P2₁/n

96.789(3)

–

2304.1(5)

P2₁/n

g [8]

V [ꢀ³]

space group

Z

2

4

1_calcd[gcm^À3

]

1.415

1.448

1.575

F

G

492

1016

1088

m

G

]

17.43

6648

18.132

13337

32.93

12528

ACHTUNGTRENNUNG

0.029

0.034

0.051

min./max. transmis- 0.588/0.811

ACHTUNGTRENNUNGsions

0.756/0.762

0.543/0.744

independent reflns 3674

observed reflns (no. 3611 (281)

variables)

4607

4279 (281)

4046

3691 (281)

refln/parameter

ratio

13.07

16.4

14.4

R₁(I>2.00s(I))

R (all reflns)

wR₂(all reflns)

GOF

0.0374

0.0406

0.1131

1.203

0.022(13)

0.69

0.0431

0.0486

0.087

1.14

–

0.41

0.0553

0.065

0.1585

1.291

–

flack parameter

max. peak in final

0.71

diff. map [eꢀ^À3

]

min. peak in final

À0.67

À0.45

À0.67

diff. map [eꢀ^À3

]

Acknowledgements

Elemental analyses were performed by Sylvia Williamson and mass spec-

trometry was performed by Caroline Horsburgh. Calculations were per-

formed by using the EaStCHEM Research Computing Facility main-

tained by Dr. H. Frꢁchtl. The work in this project was supported by the

Engineering and Physical Sciences Research Council (EPSRC). Dr. Mi-

chael Bꢁhl wishes to thank EaStCHEM for support.

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Chem. Eur. J. 2010, 16, 7617 – 7634

Article Doi

Sterically crowded peri-substituted naphthalene phosphines and their P v derivatives

DOI: 10.1002/chem.201000454

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