Reactions of ruthenium(II) tris(pyrazolyl)borate and tris(pyrazolyl) methane complexes with diphenylvinylphosphine and 3,4-dimethyl-1-phenylphosphole

.

Journal of Organometallic Chemistry 682 (2003) 272ꢁ289

/

www.elsevier.com/locate/jorganchem

Reactions of ruthenium(II) tris(pyrazolyl)borate and

tris(pyrazolyl)methane complexes with diphenylvinylphosphine and

3,4-dimethyl-1-phenylphosphole

Dee C. Wilson, John H. Nelson *

Department of Chemistry/216, University of Nevada-Reno, Reno, NV 89557-0020, USA

Received 16 May 2003; received in revised form 28 July 2003; accepted 28 July 2003

Abstract

Several new ruthenium(II) tris(pyrazolyl)borate and tris(pyrazolyl)methane complexes containing diphenylvinylphosphine

(DPVP), 3,4-dimethyl-1-phenylphosphole (DMPP) and 1,2-bis (diphenylphosphino) ethane (dppe), namely: (Tp)Ru (DPVP)

(CH₃CN)Cl; (Tp)Ru (DPVP)₂Cl; (Tp)Ru (DPVP) (DMPP) [4ꢀ2]Cl; [(Tp)Ru (DPVP)₂(CH₃CN)]PF₆; (Tp)Ru (DMPP)₂[4ꢀ2]Cl;

2]Cl]PF₆and [(Tp)Ru (dppe) (Me₂CO)]PF₆have been

/

[(Tpm)Ru (DPVP)₂Cl]PF₆; [(Tpm)Ru(dppe)Cl]PF₆; [(Tpm)Ru(DMPP)₂[4ꢀ

/

prepared, characterized and their reaction chemistry studied. Characterization includes infrared spectroscopy, H-, ¹³C{¹H}- and

1

³¹P{¹H}-NMR spectroscopy and in several cases X-ray crystallography.

Keywords: Ruthenium; Tris(pyrazolyl)borate; Tris(pyrazolyl)methane; Phosphaallyl; [4ꢀ

/

2] DielsꢁAlder cycloaddition

/

1. Introduction

kinetic lability of these species is a strong function of the

donor abilities of the ancillary ligands coordinated to

ruthenium(II).

Complexes of hemilabile bifunctional phosphine li-

gands have proven to have novel and important

applications in organometallic chemistry and in catalysis

In the course of our investigations with transition

metal complexes of olefinic phosphines we have found

that diphenylvinylphosphine (DPVP) forms the unusual

hemilabile phosphaallyl complexes [(h⁵-C₅H₅)Ru(h³-

DPVP)(h¹-DPVP)]PF₆(A) [1], [(h⁵-C₅Me₅)Ru(h³-

DPVP)(h¹-DPVP)]PF₆(B) [2], and [(h⁵-C₅H₄Me)

Ru(h³-DPVP)(h¹-DPVP)]PF₆(C) [3] (Scheme 1).

[4ꢁ

/

17]. Complexes AꢁC, and other phosphine analogs,

/

react with terminal alkynes to form vinylidene and

allenylidene derivatives that react stoichiometrically

and sometimes catalytically with a variety of nucleo-

The phosphaallyl moiety in complexes AꢁC behaves

/

as a hemilabile four-electron to two-electron donor

ligand. The major stabilizing interaction in the h³-

four-electron donor bonding mode is back donation

from the metal into the p* orbital of the vinyl group.

Consequently, both the thermodynamic stability and

philes [18ꢁ35]. The electrophilicity of the vinylidenes

/

and allenylidenes is also a strong function of the electron

density at ruthenium, which is moderated by the donor

abilities of the ancillary ligands in the metal’s coordina-

tion sphere. In order to gain additional information

regarding these important areas we have prepared new

ruthenium tris(pyrazolyl)borate and tris(pyrazo-

lyl)methane complexes as these ligands are isoelectronic

with cyclopentadiene ligands, but they possess quite

* Corresponding author. Tel.: ꢀ

/

1-775-784-6588; fax: ꢀ1-775-784-

/

6804.

different stereoelectronic properties [36ꢁ38].

/

E-mail address: jhnelson@equinox.unr.edu (J.H. Nelson).

doi:10.1016/j.jorganchem.2003.07.010

D.C. Wilson, J.H. Nelson / Journal of Organometallic Chemistry 682 (2003) 272ꢁ

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289

273

Scheme 1.

2. Results and discussion

sion is consistent with solution calorimetry measurments

by Nolan and coworkers [41] with the (h⁵-C₅Me₅)RuCl

moiety where they found a greater bond energy for

NBD than COD.

2.1. Synthesis and characterization of 1ꢁ4

/

The polymeric complexes [Ru(COD)Cl₂]_nand

[Ru(NBD)Cl₂]_n[39] (CODꢂ1,5 cylooctadiene,

NBDꢂnorbonadiene) dissolve in refluxing CH₃CN to

/

form compounds 1 and 2, respectively. Compounds 1

and 2 react further in the presence of NH₄PF₆to form 3

and 4 (Scheme 2).

All four complexes (1ꢁ

/

4) were isolated in high yield as

orangeꢁbrown crystals. Compounds 1 and 3 have been

/

previously reported [40]. Both 1 and 2 could exist in

isomeric forms with either the two chloride or two

acetonitrile ligands in mutually trans positions. Since

¹H- and ¹³C{¹H}-NMR spectroscopy would reveal

chemical shift equivalent CH₃CN molecules for both

isomers, the structure of 2 was determined by X-ray

crystallography (Fig. 1). Crystallographic data appear in

Table 1. In the molecular structure, like that of the COD

analog (1) [40], the two CH₃CN ligands occupy mu-

tually trans positions. However, for both structures the

N(1)ꢁ

1808 [167.7(2)8 (1); 165.16(12)8 (2)]. The smaller angle

for 2 correlates with somewhat shorter RuꢁC bond

distances to the coordinated diolefin [2.437(1) A (1);

˚

2.4193(11) A (ave. 2)]. Collectively, these data suggest

that NBD in sterically more bulky than COD and is

bound more strongly to ruthenium. This latter conclu-

/

Ru(1)ꢁ

/

N(2) bond angle is considerably less than

Fig. 1. Drawing of the molecular structure of 2 showing the atom-

labeling scheme. Thermal ellipsoids enclose 40% of the electron

˚

density. Hydrogen atoms have an arbitrary radius of 0.1 A. Selected

/

˚

bond distances (A) and angles (8): Ru(1)ꢁ

/

N(1), 2.045(3); Ru(1)ꢁ

Cl(2), 2.4159(11); Ru(1)ꢁ

C(7), 2.193(4); Ru(1)ꢁC(1), 2.208(4); Ru(1)ꢁ

Ru(1)ꢁN(2), 165.69(12); Cl(1)ꢁRu(1)ꢁCl(2),

/

N(2),

˚

2.053(3); Ru(1)ꢁ

C(6), 2.183(4); Ru(1)ꢁ

C(2), 2.201(4); N(1)ꢁ

92.92(4).

/

Cl(1), 2.4227(11); Ru(1)ꢁ

/

Scheme 2.

274

D.C. Wilson, J.H. Nelson / Journal of Organometallic Chemistry 682 (2003) 272ꢁ289

/

Table 1

Crystallographic data for complexes 2 and 4

Compound

Empirical formula

F_w

2

4

₁₁H₁₄Cl₂N₂Ru C₁₃H₁₇ClF₆N₃PRu

C

346.1

Triclinic

496.79

Triclinic

¯

P1

Crystal System

Space group

Unit cell dimensions

¯

P1

˚

a (A)

6.9282(8)

10.6617(18)

12.6229(18)

72.329(9)

83.600(13)

82.708(12)

878.6(2)

7.1058(18)

11.592(4)

11.986(3)

75.82(2)

87.74(2)

84.39(3)

952.5(5)

2

˚

b (A)

Scheme 3.

˚

c (A)

a (8)

b (8)

g (8)

routes. The structures of 6 and 8 are shown in Figs. 3

and 4, respectively, and crystallographic data are given

3

V (A )

˚

Z

2

1.760

1.643

r_calc(Mg m^’3)

m (mm^ꢃ1

1.732

1.104

in Table 2. For the four compounds 5ꢁ8 the ruthenium

/

coordination geometry is distorted octahedral. The Tp

and Tpm ligands occupy three facial coordination sites,

the diolefins two sites and the chloride the sixth site. For

)

Trans. Max/min

Data/restraints/parameters

GOF

R₁(F²)/wR₂(F²)

0.9668/0.8981

3073/0/182

1.029

0.9042/0.8294

3346/0/212

1.016

each structure one pyrazole ring and the RuꢁCl vector

/

0.0325/0.0723

0.0448/0.1259

define an approximate mirror plane that relates the

other two pyrazole rings and bisects the diolefin. The

˚

RuꢁCl bond lengths in the cations [2.413(2) A (5);

/

2.2. Synthesis and characterization of 5ꢁ8

/

˚

2.416(6) A (6)] are slightly shorter than those in the

˚

neutral complexes [2.4247(8) A (7); 2.4393(17) A (8)].

The ruthenium carbon bonds are shorter in the NBD

complexes than in the COD complexes again implying

Compounds 1 and 2 react cleanly with sodium or

potassium tris(pyrazolyl)borate (NaTp, KTp) and 3 and

4 (Fig. 2) react with tris(pyrazolyl)methane (Tpm) to

stronger Ruꢁ

/

NBD bonding.

The proton and carbon-NMR chemical shifts for

form 5ꢁ8 (Scheme 3).

Compounds 5 [42] and 7 [43] were previously pre-

pared by other, and in our opinion, more difficult

/

compounds 5ꢁ8 were assigned with the aid of COSY,

/

HETCOR and ¹H NOE difference spectrscopies [44].

An example of the latter is shown in Fig. 5. The

Fig. 2. Drawing of the structure of the cation of 4 showing the atom-

labeling scheme. Thermal ellipsoids enclose 40% of the electron

˚

density. Hydrogen atoms have an arbitrary radius of 0.1 A. Selected

Fig. 3. Structural drawing of 6 showing the atom-labeling scheme.

˚

bond distances (A) and angles (8): Ru(1)ꢁ

/

N(3), 2.042 (5); Ru(1)ꢁ

N(2), 2.0179 (4); Ru(1)ꢁCl(1), 2.412 (16); Ru(1)ꢁ

C(1), 2.191 (5); Ru(1)ꢁC(2), 2.202 (5); Ru(1)ꢁC(7), 2.203 (5); Ru(1)ꢁ

C(6), 2.213 (16); N(3)ꢁRu(1)ꢁN(1), 166.16 (17); N(3)ꢁRu(1)ꢁN(2),

84.02 (17); N(1)ꢁRu(1)ꢁN(2), 85.38 (17); N(3)ꢁRu(1)ꢁN(1), 78.38

(19); N(3)ꢁRu(1)ꢁCl(1), 86.03 (13); N(1)ꢁRu(1)ꢁCl(1), 86.15 (13);

N(2)ꢁRu(1)ꢁCl(1), 95.92 (13).

/

N(1),

Thermal ellipsoids enclose 40% of the electron density. Selected bond

˚

2.043 (5); Ru(1)ꢁ

/

distances (A) and angles (8): Ru(1)ꢁ

/

N(6), 2.100(5); Ru(1)ꢁ

/

N(4),

C(16),

C(11), 2.204(7); Ru(1)ꢁCl(1),

N(4), 88.3(2); N(6)ꢁRu(1)ꢁN(2), 83.4(2);

N(2), 83.4(2); N(6)ꢁRu(1)ꢁCl(1), 84.07(14); N(4)ꢁ

Cl(1), 83.06(15); N(2)ꢁRu(1)ꢁCl(1), 161.84(14).

/

2.113(5); Ru(1)ꢁ

2.213(6); Ru(1)ꢁ

2.4393(17); N(6)ꢁ

N(4)ꢁRu(1)ꢁ

Ru(1)ꢁ

/

N(2), 2.144(6); Ru(1)ꢁ

C(10), 2.208(6); Ru(1)ꢁ

Ru(1)ꢁ

/

C(15), 2.189(6); Ru(1)ꢁ

/

D.C. Wilson, J.H. Nelson / Journal of Organometallic Chemistry 682 (2003) 272ꢁ

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289

275

Fig. 4. Structural drawing of the cation of 8 showing the atom-

labeling scheme. Thermal ellipsoids enclose 40% of the electron

˚

density. Selected bond distances (A) and angles (8): Ru(1)ꢁN(4),

/

2.12(2); Ru(1)ꢁ

2.19(2); Ru(1)ꢁ

2.22(3); Ru(1)ꢁ

Ru(1)ꢁN(2), 80.8(7); N(6)ꢁ

/

N(6), 2.14(2); Ru(1)ꢁ

C(16), 2.15(2); Ru(1)ꢁ

Cl(1), 2.416(6); N(4)ꢁ

Ru(1)ꢁN(2), 82.4(8).

/

N(2), 2.140(16); Ru(1)ꢁ

C(11), 2.19(2); Ru(1)ꢁ

Ru(1)ꢁ

/

C(17),

/

/C(12),

/

N(6), 87.8(8); N(4)ꢁ

/

Table 2

Crystallographic data for complexes 6 and 8

Fig. 5. 500 MHz 1H-NMR spectrum of 5 (bottom) compared with

NOE difference spectra with irradiation of the two COD vinyl protons

(top).

Compound

Empirical formula

F_w

6

8

₁₆H₁₈BClN₆Ru C₁₇H₁₈ClF₆N₆PRu

C

441.69

Triclinic

587.86

Orthorhombic

P2₁2₁2₁

Crystal System

Space group

Unit cell dimensions

¯

P1

ment of the proton chemical shifts. The carbon chemical

shifts were then assigned via HETCOR spectroscopy.

˚

a (A)

8.2716(12)

8.9027(13)

12.2674(16)

76.233(13)

87.297(15)

78.921(17)

861.1(2)

2

10.032(2)

14.336(4)

14.793(3)

90

˚

b (A)

˚

c (A)

a (8)

b (8)

g (8)

2.3. Synthesis and characterization of 9ꢁ11

/

90

3

˚

Compound 9 was prepared according to reactions 1.

The infrared spectrum for 9

V (A )

2127.6 (8)

4

1.835

Z

r_calc(Mg m^ꢃ3

)

1.704

1.077

1ꢀKTp ^{ClCH CH Cl}

0

(Tp)Ru(COD)ClꢀKCl

m (mm^ꢃ1

Trans. Max/min

)

1.008

2

D

0.9909/0.8731

Data/restraints/paramerters 3032/0/226

0.9485/0.9038

2781/0/274

1.037

(87%)

GOF

R₁(F²) ^a/wR₂(F²) ^b

1.042

0.0507/0.0945

N₂

0

(Tp)Ru(COD)ClꢀDPVP

0.0810/0.1010

D DMF=CH₃CN

a

(Tp)Ru(DPVP)(CH₃CN)Cl (1)

9

R(F)ꢂ

wR(F)ꢂ

/

S([F_o]ꢃ

/

[F_c])/S([F_o]).

F²_c)²]/S[v(F_o²)²]]^0.5; vꢂ

b

[S[v(F²_oꢃ

/

1/s²(counts)ꢀ(rI)².

/

(80%)

shows n(Bꢁ .

H) at 2477 cm^ꢃ1and n(CN) at 2279 cm^ꢃ1

/

1

The H-NMR spectrum shows that all three pyrazole

rings are inequivalent. The vinyl proton resonances for

the coordinated DPVP ligand were clearly assigned with

the aid of an ¹H{³¹P} experiment. The ¹³C chemical

shifts were then assigned with the aid of APT and

HETCOR spectra. Compound 9 was prepared for the

purpose of studying its reactivity as illustrated in

Scheme 4. It was hoped that, as in the synthesis of the

assignment of the pyrazole H_aand H_gresonances for Tp

complexes is often ambiguous. Based upon the magni-

tudes of the Hꢁ

/

H internuclear separations measured by

˚

X-ray crystallography [H₂ꢁ

/

H_aꢂ

/

2.384 A; H₁ꢁ

/

H_aꢂ

/

˚

3.628 A; H₁ꢁ

/

H_a_?ꢂ

/

2.726 A; H₂ꢁ

/

H_a_?ꢂ4.696 A] one

/

expects to observe NOE’s between H₂and both H_aand

H_a, but only between H₁and H_a. These NOE

experiments (Fig. 5) allowed an unambiguous assign-

?

phosphaallyl complexes AꢁC that heating 9 under

/

276

D.C. Wilson, J.H. Nelson / Journal of Organometallic Chemistry 682 (2003) 272ꢁ289

/

Scheme 4.

˚

vacuum below its melting point would liberate CH₃CN

and form a phosphaallyl complex. However, after

heating this compound at 180 8C for 3 weeks under

vacuum (1 mmHg), ¹H-NMR spectroscopy revealed

that compound 9 remained unchanged. It was similarly

hoped, on the basis of an analogous reaction of (h⁶-

A] bond distance, because the former are trans to

phosphorus and the latter are trans to chloride. Phos-

Me₆C₆)Ru(DCVP)Cl₂(DCVPꢂdicyclohexylvinylpho-

/

sphine) with AgPF₆[45] in acetone that 9 would form

a phosphaallyl complex by chloride abstraction. Again 9

was recovered unchanged. Although the coordinated

CH₃CN could not be displaced intramolecularly by the

vinyl group of coordinated DPVP, complex 9 did react

cleanly with DPVP and 3,4-dimethyl-1-phenylphosphole

(DMPP) to produce 10 and 11, respectively (Scheme 4).

1

Both complexes were completely characterized by H-,

¹³C{¹H}- and ³¹P{¹H}-NMR spectroscopy and by X-

ray crystallography. The structures are shown in Figs. 6

and 7 and crystallographic data are given in Table 3.

For 10 the two Ruꢁ

/

P bond distances [Ru(1)ꢁ

/

P(1),

P(2), 2.330(3) A] are essentially the

same and very similar to those observed [46] for

Fig. 6. Structural drawing of 10 showing the atom-labeling scheme.

˚

2.340(3) A; Ru(1)ꢁ

/

Thermal ellipsoids enclose 40% of the electron density. Selected bond

˚

N(1), 2.138 (9); Ru(1)ꢁN(3), 2.153

distances (A) and angles (8): Ru(1)ꢁ

/

˚

(10); Ru(1)ꢁ

(3); Ru(1)ꢁCl(1), 2.421 (3); N(5)ꢁ

Ru(1)ꢁN(3), 89.6 (4); N(1)ꢁRu(1)ꢁN(3), 79.1 (3); N(5)ꢁ

92.3 (2); N(3)ꢁRu(1)ꢁP(2), 91.1 (2); N(5)ꢁRu(1)ꢁP(1), 91.7 (2); N(1)ꢁ

Ru(1)ꢁP(1), 90.3 (2); P(2)ꢁRu(1)ꢁP(1), 99.5 (10); P(2)ꢁRu(1)ꢁCl(1),

92.89 (11); P(1)ꢁRu(1)ꢁCl(1), 92.2 (11).

/

N(5), 2.072 (9); Ru(1)ꢁ

/

P(1), 2.340 (3); Ru(1)ꢁ

Ru(1)ꢁN(1), 87.81 (3); N(5)ꢁ

Ru(1)ꢁP(2),

/

P(2), 2.330

(Tp)Ru(PPh₃)₂Cl [Ru(1)ꢁ

/

P(1), 2.332(3) A; Ru(1)ꢁ

Cl bond distances [2.421(3) A;

2.409(3) A, respectively] are also quite similar. For 10

/

P(2),

/

˚

2.349(3) A]. The Ruꢁ

/

˚

/

˚

the Ru(1)ꢁ

/

N(1) [2.138(9) A] and Ru(1)ꢁ

/N(3) [2.153(10)

/

˚

A] bonds are both longer than the Ru(1)ꢁ

/N(5) [2.072(9)

/

D.C. Wilson, J.H. Nelson / Journal of Organometallic Chemistry 682 (2003) 272ꢁ

/

289

277

becomes a stereocenter in this reaction. The ³¹P{¹H}-

NMR spectrum exhibits only two doublets, so that this

complex is more than 99% diastereomerically pure with

the racemic R_RuR_CR_P/S_RuS_CS_Pabsolute configuration.

Thus, the cycloaddtion reaction, which is known to be

quite sensitive to steric effects, is in this case very

diastereoselective.

˚

P(1) [2.244(2) A] bond distance is

For 11 the Ru(1)ꢁ

/

˚

P(2) [2.295(3) A] distance

shorter than the Ru(1)ꢁ

/

because the 7-phosphaphosphorus is a better donor

the 2-phosphinophosphorus in all complexes of this

ligand.

2.4. Reactions of (Tp)Ru(COD)Cl with DPVP and

DMPP

Compound 10 can also be prepared directly from

(Tp)Ru(COD)Cl (reaction 2).

Fig. 7. Structural drawing of 11 showing the atom-labeling scheme.

Thermal ellispoids enclose 40% of the electron density. Selected bond

˚

N(2), 2.158 (8); Ru(1)ꢁN(4), 2.137

lengths (A) and angles (8): Ru(1)ꢁ

/

N₂

0

(7); Ru(1)ꢁ

(3); Ru(1)ꢁ

N(2), 84.9 (3); N(6)ꢁ

(3); N(6)ꢁRu(1)ꢁP(1), 94.1 (2); N(4)ꢁ

Ru(1)ꢁP(2), 93.3 (3); N(2)ꢁRu(1)ꢁP(2), 97.1 (2); P(2)ꢁ

81.32 (9); P(2)ꢁRu(1)ꢁCl(1), 96.83 (9); P(1)ꢁRu(1)ꢁCl(1), 90.76 (9).

/

N(6), 2.117 (7); Ru(1)ꢁ

Cl(1), 2.454 (2); C(14)ꢁ

Ru(1)ꢁN(4), 84.5 (3); N(6)ꢁ

Ru(1)ꢁP(1), 96.7 (2); N(6)ꢁ

Ru(1)ꢁP(1),

/

P(1), 2.244 (2); Ru(1)ꢁ

C(16), 1.343 (17); N(4)ꢁ

Ru(1)ꢁN(2), 86.2

/

P(2), 2.295

(Tp)Ru(COD)Clꢀ2DPVP

D DMF=CH₃CN

/

Ru(1)ꢁ

/

(Tp)Ru(DPVP)₂ClꢀCOD (2)

/

10 (75%)

/

It reacts with NH₄PF₆and CH₃CN to form 12 (reaction

3).

/

phine ligands have a greater trans influence than

chloride [47].

Compound 11 is not just a simple ligand substitution

10ꢀNH₄PF₆ꢀCH₃CN ^CH0²^Cl²

D

(Tp)Ru(DPVP)₂(CH₃CN)PF₆ꢀNH₄C

(3)

12 (84%)

product, but rather a [4ꢀ

/

2] DielsꢁAlder adduct of

/

DMPP and DPVP. Such intramolecular transition-

metal-promoted cycloadditions occur within the coordi-

natin spheres of a variety of metals [48]. Because of

chelation the syn-exo 2-phosphino-7-phosphanorbor-

nene is always formed, as in this case. Ruthenium

The infrared spectrum of 12 exhibits n(BH) at 2486

cm^ꢃ1and n(CN) at 2284 cm^ꢃ1similar to the values

observed for [(Tp)Ru(PPh₃)₂(CH₃CN)]PF₆(2487, 2279

cm^ꢃ1) [49] and [(Tp)Ru(dppm)(CH₃CN)]CF₃SO₃(2490,

2284 cm^ꢃ1) [42]. In an attempt to form the phosphaallyl

Table 3

Crystallographic data for complexes 10, 11 and 13

Compound

Empirical formula

F_w

10

C

11

C₃₅H₃₇BClN₆P₂Ru

749.6

13

C₃₃H₃₆BClN₆P₂Ru

725.95

₃₇H₃₆BClN₆P₂Ru

773.99

Monoclinic

P2₁/n

Crystal System

Space group

Unit cell dimensions

Monoclinic

P2₁/n

Monoclinic

P2₁/n

˚

a (A)

12.561(5)

15.659(3)

18.417(5)

90

12.0074(13)

20.055(2)

17.123(2)

90

10.542(3)

18.053(3)

17.922(4)

90

˚

b (A)

˚

c (A)

a (8)

b (8)

g (8)

105.57(3)

90

102.251(10)

90

97.82(3)

90

3

˚

V (A )

3489.5(17)

4

1.473

4029.4(8)

4

1.480

3379.1(12)

4

1.427

Z

r_calc(Mg m^ꢃ3

m (mm^ꢃ1

)

0.655

0.708

0.671

Trans. Max/min

Data/restraints/paramerters

GOF

R₁(F²)/wR₂(F²)

0.9133/0.7706

6132/0/437

1.038

0.8944/0.7615

7055/0/487

1.008

0.9350/0/0.8785

5958/0/402

1.031

0.0847/0.1848

0.0803/0.1747

0.0369/0.0709

278

D.C. Wilson, J.H. Nelson / Journal of Organometallic Chemistry 682 (2003) 272ꢁ289

/

2

complex [(Tp)Ru(h³-DPVP)(h¹-DPVP)]PF₆from 12

this complex was heated in a vacuum oven (1 mmHg)

for 3 weeks at 120 8C, just below the melting point of the

complex. However, complex 12 remained unchanged.

dimer [d 189.92 (d), 69.37 (d), J(PP)ꢂ

/

36.6 Hz] since

the ³¹P{¹H}-NMR spectra of either the [2ꢀ

/

2] or [4ꢀ4]

/

products would exhibit singlets, because of symmetry

equivalent phosphorus nuclei. The structure of 13 was

confirmed by X-ray crystallography (Fig. 8). Crystal-

lographic data are given in Table 3. The compound

possesses a distorted octahedral geometry around

Ruthenium(II) is known to promote the [2ꢀ

/

2] and

[4ꢀ2] and unusual [4ꢀ4] dimerizations of DMPP [50].

/

Thus, (Tp)Ru(COD)Cl was reacted (reaction 4) with

DMPP in order to gain more information regarding the

factors favoring each of these reaction pathways. The

³¹P{¹H}-NMR spectrum of 13 established that the

ruthenium. The Ruꢁ

/P

distances [Ru(1)ꢁ

/

P(1),

P(2), 2.2619(11) A] are not equal

as is typically found for complexes of this ligand [50ꢁ

52]. The RuꢁN distances trans to phosphorus [Ru(1)ꢁ

˚

2.2456(10) A; Ru(1)ꢁ

/

product was the [4ꢀ2]

/

˚

N(5), 2.150(3) A] are longer

N(3), 2.151(3) A; Ru(1)ꢁ

/

˚

N(1), 2.097(3) A] for

than that trans to chloride [Ru(1)ꢁ

/

reasons discussed previously.

2.5. Reactions with phenylacetylene

Terminal alkynes react with a variety of ruthenium

complexes to form vinylidene and allenylidene deriva-

tives [19]. Transition-metal vinylidene complexes are

known to be reactive intermediates in organic and

organometallic synthesis [19] as well as in the oligomer-

ization and polymerization of alkynes [20,28,29]. There

have been several ruthenium tris(pyrazolyl)borate vinyl-

idene complexes reported such as (Tp)Ru(PPh₃)Cl(ꢀ

/

Cꢀ

/

Table 4

Reduction of acetophenone to 1-phenylethanol with complexes 10, 13

and 17

Fig. 8. Drawing of the molecular structure of 13 showing the atom

numbering scheme. Phenyl carbons, except C_i, are omitted for clarity.

Thermal ellipsoids enclose 40% of the electron density. Selected bond

˚

N(1), 2.097 (3); Ru(1)ꢁN(5), 2.150

lengths (A) and angles (8): Ru(1)ꢁ

/

Entry

Substrate

Complex

t (h) % Conversion

(3); Ru(1)ꢁ

(11); Ru(1)ꢁ

1.324 (5); N(1)ꢁ

N(5)ꢁRu(1)ꢁN(3), 83.77 (11); N(1)ꢁ

Ru(1)ꢁP(1), 100.43 (8); N(1)ꢁRu(1)ꢁ

P(2), 97.40 (8); P(2)ꢁRu(1)ꢁP(1), 78.30 (4); N(5)ꢁ

86.04 (8); N(3)ꢁRu(1)ꢁCl(1), 88.22 (8); P(2)ꢁRu(1)ꢁCl(1), 92.83 (4);

P(1)ꢁRu(1)ꢁCl(1), 87.05 (4).

/

N(3), 2.151 (3); Ru(1)ꢁ

Cl(1), 2.422 (10); C(2)ꢁ

Ru(1)ꢁN(5), 83.39 (11); N(1)ꢁ

Ru(1)ꢁ

P(2), 97.80 (8); N(3)ꢁ

Ru(1)ꢁ

/

P(1), 2.246 (10); Ru(1)ꢁ

C(4), 1.330 (5); C(10)ꢁ

Ru(1)ꢁN(3), 87.85 (11);

P(1), 97.60 (8); N(5)ꢁ

Ru(1)ꢁ

Cl(1),

/

P(2), 2.262

1

2

3

4

5

6

Acetophenone

10

13

17

48

138

48

12.4

6.6

/

/C(12),

/

43.2

53.7

55.0

11.4

/

96

/

138

70

/

D.C. Wilson, J.H. Nelson / Journal of Organometallic Chemistry 682 (2003) 272ꢁ

/

289

279

CPhH) [30,53], [(Tp)Ru(PPh₃)₂(ꢀ

[ ( T p ) R u ( tm e n ) ( ꢀ C ꢀ

C Ph H )] ^ꢀ[31] ( t m e n ꢂ

(CH₃)₂NCH₂CH₂N(CH₃)₂) and [(Tp)Ru(dippe)(ꢀCꢀ

CHR)]^ꢀ[55] (dippeꢂ(ⁱPr)₂PCH₂CH₂P(ⁱPr)₂). Many

of the TpRuꢁvinylidene complexes are used for the

/

Cꢀ

/

CHR)]^ꢀ[26,54],

/

dimerization of terminal alkynes to form enynes

[26,30,34,35].

We attempted the syntheses of vinylidene complexes

by reacting complexes 10, 11 and 13 with phenylacety-

lene under a variety of conditions but in each case only

starting materials were obtained.

2.6. Catalytic hydrogenation of acetophenone

Ruthenium Tp complexes have been found to be

hydrogenation catalysts. For example, (Tp)Ru(PPh₃)

(CH₃CN)H was found to catalyze the hydrogenation of

CO₂to formic acid [56]. Chaudret and coworkers [57]

found that (Tp)Ru(COD)H is an effective hydrogena-

tion catalyst for the reduction of ketones to alcohols.

We investigated the reduction of acetophenone to 1-

phenylethanol using Kirchner’s [58] conditions (Table

4). These results show that compounds 10 and 13 are not

very effective catalysts for the hydrogenation of ketones.

Many ruthenium complexes are much better catalysts

[17,59]. We thought that this might be due to the

reluctance of these two compounds to convert to the

Fig. 9. Structural drawing of the cation of 14 showing the atom-

labeling scheme. Thermal ellipsoids enclose 20% of the electron

˚

density. Selected bond lengths (A) and angles (8): Ru(1)ꢁ

/

N(5),

P(2),

Cl(1), 2.410(15); N(5)ꢁ

N(1), 85.96(18); N(5)ꢁRu(1)ꢁ

P(2), 92.65(13); N(3)ꢁRu(1)ꢁN(1),

Ru(1)ꢁ

2.084(4); Ru(1)ꢁ

2.333(15); Ru(1)ꢁ

Ru(1)ꢁN(3), 86.14(18); N(5)ꢁ

P(1), 92.93(14); N(5)ꢁRu(1)ꢁ

/

N(3), 2.141(4); Ru(1)ꢁ

P(1), 2.410(15); Ru(1)ꢁ

Ru(1)ꢁ

/

N(1), 2.144(4); Ru(1)ꢁ

/

78.96(17);

84.37(13);

N(3)ꢁ

N(1)ꢁ

Ru(1)ꢁ

Cl(1), 91.58(5).

/

Ru(1)ꢁ

/

P(1),

92.85(13);

92.29(12);

N(3)ꢁ

N(1)ꢁ

Ru(1)ꢁCl(1), 96.12(5);

/

Cl(1),

/Ru(1)ꢁ

/

P(2),

/

/Cl(1),

88.26(13); P(2)ꢁ

/

/P(1), 95.89(5); P(2)ꢁ

/

P(1)ꢁRu(1)ꢁ

/

hydride complexes. We reacted (Tp)Ru(DMPP)₂[4ꢀ

/

2]Cl (13) with Na₂CO₃in isopropanol under catalytic

conditions but only recovered starting material. How-

phosphorus resonances were observed with a 2:1 inte-

grated ratio; a singlet at 35.7 ppm and a septet at ꢃ

142.09 ppm (¹J(PF)ꢂ

708 Hz). For 15 two resonances

also in a 2:1 integrated ratio, a singlet at 70.40 ppm and

a septet at ꢃ 707 Hz) were

143.54 ppm (¹J(PF)ꢂ

observed. For 16 three resonances in a 1:1:1 integrated

ratio, a doublet at 187.38 ppm (²J(PP)ꢂ

37.2 Hz, P₁), a

doublet at 72.47 ppm (²J(PP)ꢂ

37.2 Hz, P₂) and a septet

at ꢃ 708 Hz) were observed.

143.58 ppm (¹J(PF)ꢂ

These latter data are consistent with 16 containing a

[4ꢀ2] DielsꢁAlder dimer of DMPP as in the analog

(Tp)Ru(DMPP)₂[4ꢀ2]Cl (13).

ever, when complex 11, (Tp)Ru(DMPP)(DPVP)[4ꢀ

2]Cl, was reacted with NaBH₄in refluxing ethanol for

4 days a 91% conversion to (Tp)Ru(DMPP)(DPVP)[4ꢀ

/

2]H occurred. The presence of a hydride was established

1

by H-NMR spectroscopy. The hydride resonance was

/

observed as a doublet of doublets dꢂ

/

ꢃ13.37 ppm,

/

²J(PH)ꢂ

33, 26.5 Hz. Coupling to phosphorus was

/

1

confirmed by H{³¹P}-NMR experiments. The hydro-

genation of acetophenone to 1-phenylethanol by

/

(Tp)Ru(DMPP)(DPVP)[4ꢀ2]H was tested and found

/

that only 11% conversion was obtained after 56 h at

82 8C.

/

2.7. Tris(pyrazolyl)methane complexes

Tris(pyrazolyl)methane complexes of ruthenium [60ꢁ

/

70] have been less studied than analogous tris(pyrazo-

lyl)borate complexes. We have prepared three represen-

tative tris(pyrazolyl)methane complexes in order to

contrast and compare their properties with those of

the

tris(pyrazolyl)borate

analogs.

Accordingly,

[(Tpm)Ru(COD)Cl]PF₆(7) was reacted with DPVP,

dppe, and DMPP (reactions 5). These three complexes

were characterized by ¹H-, ¹³C{¹H}- and ³¹P{¹H}-NMR

spectroscopy.

The structure of 14 was determined by X-ray crystal-

lography (Fig. 9). Crystallographic data are given in

The latter was particularly informative. For 14 two

Table 5. As for 10 the Ru(1)ꢁ

/

N(3) and Ru(1)ꢁN(1)

/

280

D.C. Wilson, J.H. Nelson / Journal of Organometallic Chemistry 682 (2003) 272ꢁ289

/

Table 5

Crystallographic data for complexes 14, 15 and 17

Compound

Empirical formula

F_w

14

C

16

C₃₆H₂₉ClF₆N₆P₃Ru

888.6

17

C₃₉H_41.5BF₆N₆O_1.5P₃Ru

₃₈H₃₆ClF₆N₆P₃Ru

919.2

Triclinic

937.07

Monoclinic

C2/c

Crystal System

Space group

Unit cell dimensions

Monoclinic

P2₁/n

¯

P1

˚

a (A)

11.9453(12)

13.2256(13)

14.2944(12)

99.993(9)

101.794(9)

97.244(12)

2146.3

9.882(2)

25.268(3)

18.636(3)

90

34.344(7)

12.720(3)

20.482(6)

90

˚

b (A)

˚

c (A)

a (8)

b (8)

100.31(2)

90

96.50(3)

90

g (8)

3

V (A )

˚

4578.1(13)

4

1.351

8890(4)

8

1.400

Z

2

1.514

0.606

r_calc(Mg m^ꢃ3

m (mm^ꢃ1

)

0.565

0.524

Trans. Max/min

Data/restraints/paramerters

GOF

R₁(F²) ^a/wR₂(F²) ^b

0.964/0.8808

7556/0/532

1.050

0.9663/0.9133

8057/0/254

1.064

ꢁ

/

5804/0/565

1.018

0.0753/0/0.1659

0.0576/0.1254

0.0803/0.2079

a

R(F)ꢂ

wR(F)ꢂ

/

S([F_o]ꢃ

/

[F_c])/S([F_o]).

F²_c)²]/S[v(F_o²)²]]^0.5; vꢂ

b

[S[v(F²_oꢃ

/

1/s²(counts)ꢀ(rI)².

/

Fig. 10. Structural drawing of the cation of 15 showing the atom-

labeling scheme. Thermal ellipsoids enclose 20% of the electron

˚

Fig. 11. Structural drawing of the cation of 17 showing the atom-

labeling scheme. All phenyl carbons, except C_i, are omitted for clarity.

density. Selected bond distances (A) and angles (8): Ru(1)ꢁ

/

N(2),

P(1),

N(4), 83.4(3); N(2)ꢁ

N(6), 85.3(4); N(2)ꢁRu(1)ꢁP(1),

P(2), 96.2(2); N(6)ꢁRu(1)ꢁP(1), 96.7(2); N(6)ꢁ

P(2), 94.6(3); P(1)ꢁRu(1)ꢁP(2), 84.46(11).

2.141(8); Ru(1)ꢁ

2.313(3); Ru(1)ꢁ

Ru(1)ꢁN(6), 85.7(3); N(4)ꢁ

95.9(2); N(4)ꢁRu(1)ꢁ

Ru(1)ꢁ

/

N(4), 2.124(8); Ru(1)ꢁ

P(2), 2.287(3); N(2)ꢁRu(1)ꢁ

Ru(1)ꢁ

/

N(6), 2.090(8); Ru(1)ꢁ

/

Thermal ellipsoids enclose 40% of the electron density. Selected bond

˚

/

distances (A) and angles (8): Ru(1)ꢁ

/

N(2), 2.141(9); Ru(1)ꢁ

/

N(4),

P(2),

N(6), 86.5(3);

P(2), 96.0(3); N(4)ꢁRu(1)ꢁ

P(2), 93.8(3); N(6)ꢁRu(1)ꢁP(1), 92.2(3);

/

2.064(9); Ru(1)ꢁ

2.300(3); N(2)ꢁRu(1)ꢁ

N(4)ꢁRu(1)ꢁN(6), 86.9(4); N(2)ꢁ

P(1), 94.5(3); N(4)ꢁRu(1)ꢁ

P(1)ꢁRu(1)ꢁP(2), 85.2(11).

/

N(6), 2.137(9); Ru(1)ꢁ

N(4), 84.2(4); N(2)ꢁ

Ru(1)ꢁ

/

P(1), 2.302(3); Ru(1)ꢁ

/

Ru(1)ꢁ

/

bond distances are longer than the Ru(1)ꢁ

tances due to the trans influence of the phosphine

ligands trans to N(1) and N(3). The RuꢁP and RuꢁCl

distances differ very little between the two compounds.

However, the P(2)ꢁRu(1)ꢁP(1) bond angles [95.89(5)8,

14; 99.51(10)8, 10], P(2)ꢁRu(1)ꢁCl(1) angles [96.15(5)8,

14; 92.89(11)8, 10] and P(1)ꢁRu(1)ꢁCl(1) [91.58(5)8, 14;

/N(5) dis-

/

92.2(11)8, 10] differ considerably suggesting that the

steric bulk of the Tp and Tpm ligands is quite different.

A measure of the steric bulk of a ligand is the Tolman

cone angle [71]. The cone angles calculated from the

crystal structures of 10 and 14 are: Tp(1808), Tpm

/

D.C. Wilson, J.H. Nelson / Journal of Organometallic Chemistry 682 (2003) 272ꢁ

/

289

281

(1708). This shows that tris(pyrazolyl)borate is sterically

larger than tris(pyrazolyl)methane.

4. Experimental

4.1. Reagents and physical measurements

The crystal structure of 15 (Fig. 10) was also

determined in order to compare the structure of

[(Tpm)Ru(dppe)Cl]PF₆(15) with that of an analogous

Tp containing cation, [(Tp)Ru(dppe)(Me₂CO)]PF₆(17)

(Fig. 11) that we prepared according to reactions (6).

All Chemicals were reagent grade and were used as

received or synthesized as described below. NaTp [36],

KTp [36], Tpm [76], DPVP [77], DMPP [78], [Ru(COD)

Cl₂]_n[39], [Ru(NBD)Cl₂]_n[39], [Ru(COD)(CH₃CN)₂

Cl₂] [40] and [Ru(COD)(CH₃CN)₃Cl]PF₆[40] were

synthesized by literature procedures. Solvents were dried

by standard procedures [79]. Elemental analyses were

performed by Galbraith Laboratories, Knoxville, TN.

Melting points were obtained using a Mel-Temp appa-

ratus and are uncorrected. NMR spectra were recorded

on a Varian Unity Plus 500 FT-NMR spectrometer

operating at 499.8 MHz for ¹H, 125.7 MHz for ¹³C{¹H}

and 202.3 MHz for ³¹P{¹H}. Proton and carbon

chemical shifts are relative to internal Me₄Si, while

phosphorus chemical shifts are relative to external 85%

H₃PO₄(aq) with positive values being downfield of the

respective reference. FT-IR spectra were obtained as

thin films or Nujol mulls on NaCl windows on a

(Tp)Ru(COD)Clꢀdppe ^D0^MF(Tp)Ru(dppe)ClꢀCOD

D

(52%)

(Tp)Ru(dppe)ClꢀAgPF₆^M0^e²^CO

[(Tp)Ru(dppe)(Me₂CO)]PF₆ꢀAgCl (6)

17 (70%)

Crystallographic data are given in Table 5. The Ruꢁ

and RuꢁN distances in the two compounds are nearly

the same. The RuꢁN distances trans to chloride in 16

/P

/

˚

[2.090(8) A] and trans to oxygen in 17 [2.064(9) A] are

nearly equal and shorter than all the RuꢁN distances to

/

Perkinꢁ

graphy mass-spectra, GCMS, were recorded on a

HewlettꢁPackard 59970 gas chromatograph; 20% DC

/

Elmer 2000 Ft-IR spectrometer. Gas chromato-

nitrogens trans to phosphorus.

/

200 Chromosorb P (10.16, 0.64 cm) or HP-1 (cross

linked methyl siloxane) columns (2.5 m, 0.11 m) were

used.

3. Concluding remarks

Several new ruthenium(II) tris(pyrazolyl)borate and

tris(pyrazolyl)methane complexes containing DPVP and

DMPP have been prepared and completely character-

ized. Attempts at forming phosphaallyl derivatives from

various DPVP complexes were all unsuccessful. This

could be due to an insufficient electron donor ability for

both Tp and Tpm, as we have shown that electron rich

ruthenium(II) centers are necessary to stabilize the

h³-DPVP phosphaallyl bonding mode by p-back dona-

tion into the vinyl p* orbital. It has been demonstrated

that toward ruthenium(II) the Tp ligand is less electron

donating than Cp [38]. This has been argued on the basis

of comparative values of n(CO) in ruthenium carbonyl

complexes. For example, (Tp)Ru(PPh₃)(CO)Cl has

n(CO) at 1965 cm^ꢃ1while (Cp)Ru(PPh₃)(CO)Cl has

n(CO) at 1958 cm^ꢃ1[72]. The inability to remove

CH₃CN thermally or to be displaced by terminal

alkynes in these complexes is consistent with the

stabilities of other ruthenium tris(pyrazolyl)borate

acetonitrile complexes. For example, the stability of

4.2. Synthesis

4.2.1. Ru(NBD)(CH₃CN)₂Cl₂(2)

CH₃CN (215 ml) was added to {RuCl₂(NBD)}_n

(7.575g, 28.68 mmol). In order to suppress the forma-

tion of RuCl₂(NCCH₃)₄, norbornadiene (4.6 ml, 42.64

mmol) was added. The mixture was heated at reflux for

5 h. The mixture was then filtered hot to

remove unreacted {RuCl₂(NBD)_n}. The volume of the

filtrate was concentrated to 100 ml, and the mixture was

brown

crystals.

placed in a freezer overnight to yield orangeꢁ

/

the complexes [(Tp)Ru(tmeda)L]^ꢀ(tmedaꢂ

CH₂NMe₂) was found to increase with L in the order

LꢂTHFBCF₃SO₃BacetoneBCH₃CN:DMF [73].

These workers also found that the CH₃CN exchange

rate is more than eight orders of magnitude slower for

[(Tp)Ru(CH₃CN)₃]^ꢀthan for [(Cp)Ru(CH₃CN)₃]^ꢀ

[74,75].

/Me₂NCH₂

/

Yield 4.399 g (44.3%). X-ray quality crystals were grown

by slow recrystallization from acetonitrile. IR (Nujol):

2320 cm^ꢃ1n(CN). M.p.ꢂ

150 8C dec without melting.

Anal. Calc. for C₁₁H₁₄Cl₂N₂Ru: C, 38.16; H, 4.08; Cl,

/

1

20.48. Found: C, 37.95; H, 4.16; Cl, 20.34%. H-NMR

282

D.C. Wilson, J.H. Nelson / Journal of Organometallic Chemistry 682 (2003) 272ꢁ289

/

(499.8 MHz, 258C, CDCl₃): d 4.78 (s, 4H, H₂),

3.85 (s, 2H, H₁), 2.72 (s, 6H, CH₃CN), 1.53 (s, 2H,

H₃). ¹³C{¹H}-NMR (125.7 MHz, 25 8C, CDCl₃):

(n_BꢁH), m.p.: 195 8C dec.

d 126.94 (s, 2C, CH₃CN), 72.36 (s, 4C, Cꢀ

/

C, C₂),

61.18 (s, 2C, C₁), 49.23 (s, 1C, C3), 6.66 (s, 2C,

4.2.4. (Tp)Ru(NBD)Cl (6)

A mixture containing Ru(NBD)(CH₃CN)₂Cl₂(2.06 g,

5.95 mmol) and NaTp (1.72 g, 7.29 mmol) was heated at

reflux in 1,2-dichloroethane (50 ml) for 3 h. The solvent

CH₃CN).

was removed by rotary evaporation to leave a brownꢁ

/

4.2.2. [Ru(NBD)(CH₃CN)₃Cl]PF₆(4)

orange solid. The solid was washed with acetone and the

orange solid was isolated by filtration. Yield: 1.861 g

(70.8%). X-ray quality crystals were obtained from

An acetonitrile solution (50 ml) containing

Ru(NBD)(CH₃CN)₂Cl₂(1.886 g, 5.45 mmol) and

NH₄PF₆(1.923 g, 11.80 mmol) was heated at reflux

for 15 min. The solution was then cooled to room

temperature (r.t.), and the insolubles were removed by

filtration. The volume of the filtrate was concentrated to

one half the original volume, and absolute ethanol (50

ml) and ether (100 ml) were added. The solution was

then cooled in a freezer overnight during which time

yellow-needle crystals precipitated out and were isolated

CH₂Cl₂ꢁEt₂O. M.p: 227 8C dec. Anal. Calc. for

/

C₁₆H₁₈BClN₆Ru: C, 43.51; H, 4.11; Cl, 8.03. Found:

C, 43.36; H, 4.23; Cl, 7.89%. IR (Nujol) 2481 cm^ꢃ1

n(BH). ¹H-NMR (499.8 MHz, 25 8C, CDCl₃): d 8.43 (d,

³J(H_a?H_b?)ꢂ

/

2.0 Hz, 1H, H_a?), 7.76 (d, ³J(H_g?H_b?)ꢂ

/

2.5

2.0 Hz, 2H, H_g), 7.30

2.0 Hz, 2H, H_a), 6.33 (apparent t,

2.5 Hz., ³J(H_b?H_a?)ꢂ

2.0 Hz, 1H, H_b?),

J(H_bH_a)ꢂ2.0 Hz, 2H,

J(H₃H₄)ꢂ5.0 Hz,

J(H₂H₁)ꢂ4.5

Hz, 1H, H_g?), 7.64 (d, ³J(H_gH_b)ꢂ

(d, ³J(H_aH_b)ꢂ

³J(H_b?H_g?)ꢂ

/

by filtration. Yield 1.803 g (67%). M.p.ꢂ

/

171 8C dec.

6.16 (apparent t, ³J(H_bH_g)ꢂ³

/

3

Anal. Calc. for C₁₃H₁₇ClF₆N₃PRu: C, 31.43; H, 3.45;

Cl, 7.14. Found: C, 31.29; H, 3.51; Cl, 7.20%. IR

(Nujol): 2335 cm^ꢃ1n(CN). ¹H-NMR (499.8 MHz,

25 8C, CD₃NO₂): d 5.12 (m, 2H, H₂), 4.97 (m, 2H,

H₃), 3.94 (m, 2H, H_1,4), 2.74 (s, 6H, 2CH₃CN e), 2.43 (s,

H_b), 5.28 (apparent t, J(H₃H₂)ꢂ³

/

2H, H₃), 4.44 (apparent t, J(H₂H₃)ꢂ³

/

3

Hz, 2H, H₂), 4.25 (mult., 2H, H _1,4), 1.70 (apparent t,

³J(H₅H₁)ꢂ³1.5 Hz, 2H, H₅). ¹³C{¹H}-

/

J(H₅H₄)ꢂ

/

NMR (125.7 MHz, 25 8C, CDCl3): d 144.90 (s, 1C,

C_a?), 140.95 (s, 2C, C_a), 137.05 (s, 1C, C^g?), 134.60 (s,

2C, C_g), 106.24 (s, 1C, C_b?), 105.80 (s, 2C, C_b), 80.21 (s,

2C, C₃), 70.27 (s, 2C, C₂), 60.21 (s, 1C, C₅), 52.52 (s, 1C,

C₁), 51.25 (s, 1C, C₄).

3H, CH₃CN a), 1.54 (t, ³J(HH)ꢂ

/

1.5 Hz), 2H, H₅).

¹³C{¹H}-NMR (125.7 MHz, 25 8C, CD₃NO₂):

d

129.52 (s, 2C, CH₃CN e), 125.34 (s, 1C, CH₃CN a),

79.89 (s, 2C, C₂), 75.55 (s, 2C, C₃), 61.65 (s, 1C, C₅),

49.63 (s, 2C, C_1,4), 3.06 (s, 2C, CH₃CN e), 1.99 (s, 1C,

CH₃CN a).

4.2.5. [(Tpm)Ru(COD)Cl]PF₆(7)

A solution of [Ru(COD)(CH₃CN)₃Cl]PF₆(3.52 g,

6.87 mmol) and Tpm (1.47 g, 6.87 mmol) in 1,2-

dichloroethane (35.0 ml) was heated at reflux for 3 h.

During this time an orange solid formed which was

isolated by filtration to obtain 7. Yield: 2.03 g (49%). X-

4.2.3. (Tp)Ru(COD)Cl (5)

A mixture of Ru(COD)(CH₃CN)₂Cl₂(0.817 g, 2.26

mmol) and KTp (0.574 g, 2.28 mmol) in 50 ml of 1,2-

dichloroethane was heated at reflux overnight. The

solution was then cooled and the solid KCl was removed

by filtration over Celite. The solvents were removed by

rotary evaporation to obtain an orange solid. Yield

0.901 g (86.6%). X-ray quality crystals were obtained

ray quality crystals were obtained from acetoneꢁEt₂O.

/

¹H-NMR (499.8 MHz, d, acetone, 25 8C): 9.68 (s, 1H,

3

?

HCN₃), 8.73 (d, J(H_a,b?)ꢂ

/

2.5 Hz, 1H, H_a?), 8.68 (dd,

4

³J(H_g,b?)ꢂ

/

3.0 Hz, J(H_g,a?)ꢂ

/

0.50 Hz, 1H, H_g?), 8.50

0.50 Hz, 2H, H_g), 8.01

?

from CH₂Cl₂ꢁ

/

hexane. ¹H-NMR (499.8 MHz, d,

(dd, ³J(H_g,b)ꢂ

/

2.5 Hz, ⁴J(H_g,a)ꢂ

/

5

3

CD₂Cl₂, 25 8C): 8.18 (d, ³J(H_a?H_b?)ꢂ

/

2.50 Hz, 1H,

?

(apparent dt, J(H_a,HCN)ꢂ

/

1.0 Hz, J(H_a,b)ꢂ

/

2.0 Hz,

?

3

H_a?), 7.84 (dd, J(H_b?,g?)ꢂ

/

2.0 Hz, 4J(H_g,a?)ꢂ

/

0.50 Hz,

0.50

⁴J(H_a,g)ꢂ

/

0.50 Hz, 2H, H_a), 6.82 (dd, J(H_bg?)ꢂ

/

2.5

2.6

3

1H, H_g?), 7.71 (dd, ³J(H_g,b)ꢂ

/

2.5 Hz, ⁴J(H_g,a)ꢂ

2.0 Hz, 2H, H_a), 6.36

/

Hz, J(H_ba?)ꢂ

/

2.5 Hz, 1H, H_b?), 6.65 (dd, ³J(H_b,g)ꢂ

/

?

3

Hz, 2H, H_g), 7.56 (d, J(H_a,b)ꢂ

/

Hz, J(H_b,a)ꢂ3.0 Hz, 2H, H_b), 5.06 (m, 2H, H₁), 4.29

/

3

?

(apparent t, J(H_b,g?)ꢂ

/

2.5 Hz, J(H_b,a?)ꢂ

/2.0 Hz, 1H,

(m, 2H, H₂), 2.85 (m, 2H, H₃), 2.50 (m, 2H, H₅), 2.36

(m, 2H, H₆), 2.21 (m, 2H, H₄). ¹³C{¹H}-NMR (125.7

MHz, d, acetone-d₆, 25 8C): 150.62 (s, 1C, C_a?), 146.94

(s, 2c, C_a), 138.34 (s, 1C, C_g?), 135.07 (s, 2C, C_g), 110.40

(s, 1C, C_b?), 109.65 (s, 2C, C_b), 96.63 (s, 2C, C₁), 89.69

(s, 2C, C₂), 77.23 (s, 1C, HCN), 29.99 (CH₂’s). ³¹P{¹H}

3

H_b?), 6.24 (apparent t, J(H_b,g)ꢂ

/

2.5 Hz, J(H_b,a)ꢂ2.0

/

Hz, 2H, H_b), 4.85 (m, 2H, H₁), 4.00 (m, 2H, H₂), 2.90

(m, 2H, H₃), 2.70 (m, 2H, H₅), 2.43 (m, 2H, H₆), 2.27

(m, 2H, H₄). ¹³C{¹H}-NMR (125.7 MHz, d, CD₂Cl₂,

25 8C): 145.80 (s, 1C, C_a?), 142.37 (s, 2C, C_a), 138.17 (s,

1C, C_g?), 135.39 (s, 2C, C_g), 106.76 (s, 1C, C_b?), 106.35

(s, 2C, C_b), 94.92 (s, 2C, C₁), 87.42 (s, 2C, C₂), 30.83 (s,

2C, C₄), 30.27 (s, 2C, C₃). IR (Nujol, cm^ꢃ1): 2502

(202.3 MHz, d, acetone, 25 8C): ꢃ

/

142.96 (septet,

¹J(PF)ꢂ

/

706 Hz, PF₆). M.p.ꢂ222 8C dec.

/

D.C. Wilson, J.H. Nelson / Journal of Organometallic Chemistry 682 (2003) 272ꢁ

/

289

283

3

2

4.2.6. [(Tpm)Ru(NBD)Cl]PF₆(8)

³J(H_aH_c)ꢂ

/

18.3 Hz, J(PH)ꢂ

/

16.5 Hz, J(H_bH_c)ꢂ

/

2.0

Hz, 1H, H_c), 1.94 (s, 3H, CH₃). ³¹P{¹H}-NMR (202.3

A mixture containing [Ru(NBD)(CH₃CN)₃Cl]PF₆

(0.715 g, 1.51 mmol) and Tpm (0.383 g, 1.79 mmol)

was heated at reflux in 1,2-dichloroethane (15 ml) for 3

h. The resulting orange solid was isolated by filtration.

The orange solid was extracted with acetone, and the

insolubles were removed by filtration. The solvent was

then removed by rotary evaporation. Recrystallization

MHz, CD₂Cl₂, 25 8C): d 46.78. ¹³C{¹H}-NMR (125.7

MHz, CD₂Cl₂, 25 8C): d 145.57 (d, ³J(PC)ꢂ

/

1.0 Hz,

C_a), 145.54 (d, ³J(PC)ꢂ

/

1.4 Hz, C_a), 142.51 (s, C_a),

1

136.68 (d, J(PC)ꢂ

30.9 Hz, C_a?), 136.36 (2C, C_g), 135.70 (d, J(PC)ꢂ

Hz, C_o), 134.99 (d, ⁴J(PC)ꢂ

2.0 Hz, C_g), 132.41 (d,

²J(PC)ꢂ

8.5 Hz, C_o), 130.26 (d, J(PC)ꢂ

129.68 (d, ¹J(PC)ꢂ40.5 Hz, C_i), 129.07 (d, ⁴J(PC)ꢂ

/

41.7 Hz, C_i), 136.54 (d, J(PC)ꢂ

/

2

/10.3

/

4

from nitromethaneꢁether afforded orange crystals.

/

2.1 Hz, C_p),

Yield 0.376 g (42%). Anal. Calc. for C₁₇H₁₈ClF₆N₆PRu:

C, 34.73; H, 3.09; Cl, 6.03. Found: C, 34.65; H, 3.18; Cl,

/

2.0

3

Hz, C_p), 128.68 (d, J(PC)ꢂ

/

8.5 Hz, C_m), 128.03 (d,

3.8 Hz, C_b?),

1

6.12%. H-NMR (499.8 MHz, 25 8C, CD₃NO₂): d 9.05

³J(PC)ꢂ

/

9.2 Hz, C_m), 127.04 (d, J(PC)ꢂ

/

2

3

(s, 1H, HCN₃), 8.88 (d, J(H_a?H_b?)ꢂ

/

2.0 Hz, 1H, H_a?),

121.50 (s, CH₃CN), 106.32 (s, C_b), 105.99 (s, C_b), 105.98

(s, C_b), 4.00 (CH₃CN). IR (Nujol, cm^ꢃ1): 2477 (m,

n(BH)), 2279 (m, n(CN)).

8.45 (d, ³J(H_g?H_b?)ꢂ

/

2.5 Hz, 1H, H_g?), 8.31 (d,

2.5 Hz, J(H_gH_a)ꢂ1.0 Hz, 2H, H_g), 7.68

(d, ³J(H_aH_b)ꢂ

2.5 Hz, 2H, H_a), 6.75 (apparent t,

³J(H_b?H_g?)ꢂ2.5 Hzꢂ³

J(H_b?H_a?)ꢂ2.5 Hz, 1H, H_b?),

6.56 (apparent t, ³J(H_bH_g)ꢂ2.5 Hz, ³J(H_bH_a)ꢂ

2.0

Hz, 2H, H_b), 5.50 (apparent t, ³J(H₃H₂)ꢂ

4.0 Hz,

³J(H₃H₄)ꢂ

3.5 Hz, 2H, H₃), 4.91 (apparent t,

³J(H₂H₃)ꢂ

(mult., 1H, H ), 4.16 (m, 1H, H₄), 1.79 (apparent t,

4

³J(H_gH_b)ꢂ

/

4.2.8. (Tp)Ru(DPVP)₂Cl (10)

/

3

/

4.0 Hz, J(H₂H₁)ꢂ3.0 Hz, 2H, H₂), 4.45

/

1

³J(H₅H₁)ꢂ³

/

J(H₅H₄)ꢂ

1.5 Hz, 2H, H₅). ¹³C{¹H}-

/

NMR (125.7 MHz, 25 8C, CD₃NO₂): d 149.54 (s, 1C,

C_a?), 145.46 (s, 2C, C_a), 136.26 (s, 1C, C^g?), 133.49 (s,

2C, C_g), 109.03 (s, 1C, C_b?), 108.518 (s, 2C, C_b), 82.05 (s,

2C, C₃), 76.55 (s, 1C, HCN₃), 72.83 (s, 2C, C₂), 60.71 (s,

1C, C₅), 52.43 (s, 1C, C₁), 50.98 (s, 1C, C₄).

A suspension of (Tp)Ru(COD)Cl (286 mg, 0.624

mmol) and diphenylvinylphosphine, DPVP, (213 mg,

4.2.7. (Tp)Ru(DPVP)(CH₃CN)Cl (9)

1.01 mmol) was heated at reflux for 20 h in a 1:1 DMFꢁ

/

A solution containing (Tp)Ru(COD)Cl (1.00g, 2.18

mmol) and DPVP (0.6 ml, 3.02 mmol) in CH₃CN (15

ml) and DMF (20 ml) was heated at reflux for 24 h

under an atmosphere of nitrogen. The solvent was then

removed be vacuum distillation to obtain a yellow

residue. The residue was dissolved in a miminum

amount of CH₂Cl₂. Hexane was added and the resulting

yellow solid was isolated by filtration. Yield: 0.423 g

CH₃CN (12 ml) mixture. After removal of the solvents

in vacuo a bright yellow solid was obtained. Yield 360

mg (74.6%). X-ray quality crystals were obtained after

recrystallization from CH₂Cl₂/ꢁC₂H₅)₂O. Anal. Calc.

/

for C₃₇H₃₆BClN₆P₂Ru: C, 57.27; H, 4.68. Found: C,

1

57.01; H, 4.81%. H-NMR (499.8 MHz d, CD₂Cl₂, 25

8C): 7.92 (d, ³J(H_g?H_b?)ꢂ

/

2.5 Hz, 1H, H_g?), 7.64 (d,

2.5 Hz, 2H, H_g), 7.39 (m, 2H, H_p), 7.35 (m,

4H, H_m), 7.24 (m, 4H, H_o), 7.16 (m, 2H, H_p), 7.14 (d,

³J(H_a?H_b?)ꢂ

2.0 Hz,1H, H_a?), 6.96 (m, 6H, H_mꢀH_a),

6.59 (m, 4H, H_o), 6.50 (m, 2H, H_a), 5.92 (t, J(H_a?H_b?)

2.0 Hz, ³J(H_g?H_b?)ꢂ

2.5 Hz, 1H, H_b?), 5.80 (t,

2.5 Hz, 2H, H_b), 5.76

³J(H_gH_b)ꢂ

/

(33%).

C₂₅H₂₆BClN₇PRu: C, 49.81; H, 4.35; N, 16.26. Found:

M.p.ꢂ

/

215 8C.

Anal.

Calc.

for

C, 49.57; H, 4.60; N, 16.13. ¹H-NMR (499.8 MHz,

/

CD₂Cl₂, 25 8C): d 7.97 (dd, ³J(H_gH_b)ꢂ

/

2.0 Hz, 1H,

24.0 Hz, ³J(H_aH_c)ꢂ

18.3 Hz,

12.0 Hz, 1H, H_a), 7.80 (dd, J(H_gH_b)ꢂ2.0

Hz, ⁴J(H_gH_a)ꢂ0.5 Hz, 1H, H_gb), 7.75 (dd, ³J(H_gH_b)ꢂ

2.5 Hz, ⁴J(H_gH_a)ꢂ

0.5 Hz, 1H, H_gc), 7.74 (app dt,

³J(H_bH_a)ꢂ2.5 Hz, ⁴J(H_gH_a)ꢂ⁴

J(PH)ꢂ0.5 Hz, 1H,

H_aa), 7.66 (dd, J(H_bH_a)ꢂ2.0 Hz, J(H_gH_a)ꢂ0.5 Hz,

1H, H_ab), 7.63 (m, 2H, H_o), 7.49 (m, 2H, H_m), 7.46 (m,

1H, H_p), 7.01 (m, 2H, H_m), 6.91 (d, ³J(H_bH_a)ꢂ

2.0 Hz,

1H, H_ac), 6.59 (m, 2H, H_o), 6.28 (ddd, J(H_bH_a)ꢂ2.5

Hz, ³J(H_gH_b)ꢂ2.0 Hz, ⁵J(PH)ꢂ

1.0 Hz, H_ba), 6.06 (dd,

³J(H_bH_a)ꢂ

2.5 Hz, J(H_gH_b)ꢂ2.0 Hz, 1H, H_bb), 6.00

(ddd, ³J(PH)ꢂ32.5 Hz, ³J(H_aH_b)ꢂ

12.0 Hz,

²J(H_bH_c)ꢂ

2.0 Hz, 1H, H_b), 5.94 (dd, J(H_bH_a)ꢂ2.5

Hz, ³J(H_gH_b)ꢂ

2.0 Hz, 1H, H_bc), 4.97 (ddd,

3

H_ga), 7.83 (ddd, ²J(PH)ꢂ

³J(H_aH_b)ꢂ

/

ꢂ

/

3

/

³J(H_aH_b)ꢂ

/

2.0 Hz, J(H_gH_b)ꢂ

/

3

/

(m, 2H, H_b), 4.91 (m, 2H, H_c). ³¹P{¹H} (d, CD₂Cl₂,

202.3 MHz, 25 8C): 22.32 (s, 2P, DPVP). ¹³C{¹H}

(125.7 MHz d, CD₂Cl₂, 25 8C): 149.36 (s, C_a?), 145.04 (s,

/

3

4

/

C_a), 137.37 (s, C_b), 136.26 (m, [²J(PC_o)ꢀ⁴

/

J(PC_o]ꢀ

235.5 Hz, C_a), 135.14

(s, C_g), 133.49 (s, C_o), 132.67 (d, [¹J(PC_i)ꢀ³

J(PC_i)]ꢂ

40.2 Hz, C_i), 130.01 (s, C_p?), 129.11 (s, C_p), 128.07 (t,

/

C_g?ꢀ

/

C_i), 136.20 (d, ¹J(PC_a)ꢂ

/

3

/

[³J(PC_m)ꢀ⁵

/

J(PC_m)]ꢂ

/

14.5 Hz, C_m), 127.77 (t,

3

/

16.0 Hz, C_m), 105.74 (s, C_b?),

/

105.50 (s, C_b). IR (Nujol, cm^ꢃ1): 2476 (m, n_BꢁH). MP:

145 8C.

3

/

284

D.C. Wilson, J.H. Nelson / Journal of Organometallic Chemistry 682 (2003) 272ꢁ289

/

4.2.9. (Tp)Ru(DPVP)(DMPP)[4ꢀ

/

2]Cl (11)

30.3 Hz, ²J(PC)ꢂ

31.2 Hz, C₄), 36.76 (dd, ¹J(PC)ꢂ

29.9 Hz, C₂), 29.29 (dd, ²J(PC)ꢂ

5.7 Hz, C₃), 15.27 (s, CH₃₍₅₎), 13.90 (d, ³J(PC)ꢂ

Hz, CH₃₍₆₎).

/

10.8 Hz, C₁), 47.44 (d, ¹J(PC)ꢂ

35.4 Hz, ²J(PC)ꢂ

12.9 Hz, ²J(PC)ꢂ

1.9

/

4.2.10. (Tp)Ru(DPVP)(DMPP)[4ꢀ

An ethanol solution containing RuTp(DPVP)

(DMPP)[4ꢀ2]Cl (0.200 g, 0.267 mmol) and NaBH₄

/

2]H

/

(0.0947, 2.5 mmol) was heated at reflux for 4 days. The

solution was cooled to r.t. and the insolubles were

removed by filtration. The solvent was removed by

rotary evaporation to obtain a light colored solid. Yield

1

0.1238 g (65%). H-NMR (499.8 MHz, 25 8C, C₆D₆): d

8.54 (app t, ³J(H_oP)ꢂ

/

8.0 Hz, ³J (H_oH_m)ꢂ

/

5.0 Hz, 2H,

H_o), 8.01 (d, ³J(H_aH_b)ꢂ

³J(H_gH_b)ꢂ2.5 Hz, 1H, H_g), 7.49 (d, ³J(H_gH_b)ꢂ

Hz, 1H, H_g), 7.38 (d, J(H_aH_b)ꢂ

/

1.5 Hz, 1H, H_a), 7.57 (d,

A solution containing (Tp)Ru(DPVP)(CH₃CN)Cl

(0.239 g, 0.397 mmol) and DMPP (0.1 ml, 0.53 mmol)

was heated at reflux in 1,2-dichloroethane (100 ml)

under an atmosphere of nitrogen for 20 h. The solvent

was then removed to obtain a red residue. The residue

was dissolved in a minimum amount of CH₂Cl₂. Hexane

was added to the CH₂Cl₂solution and the resulting

yellow solid was isolated by filtration to obtain 11. Yield

0.214 g (69.6%). Anal. Calc. for C₃₅H₃₆BClN₆P₂Ru: C,

56.05; H, 4.84. Found: C, 55.92; H, 4.93%. X-ray quality

crystals were obtained by recrystallization from CH₂Cl₂/

/

/2.0

3

/

2.5 Hz, 1H, H_a), 7.32

3

(m, 4H, H_m), 6.96 (m, 3H, H_p), 6.86 (d, J(H_aH_b)ꢂ

/2.0

Hz, 1H, H_a), 6.78 (m, 6H, H_o,m), 5.83 (appt t,

³J(H_bH_g)ꢂ³

/

J(H_bH_a)ꢂ

/

2.5, Hz, 1H, H_b), 5.76 (app t,

2.0 Hz, 1H, H_b), 5.61 (app t,

2.5 Hz, 1H, H_b), 3.09 (bs, 1H,

/

H₅), 2.09 (s, 1H, H₁), 2.65 (m, 1H, H₃), 2.56 (bs, 1H,

H₂), 1.57 (s, 3H, CH₃), 1.40 (s, 3H, CH₃), 1.09 (m, 1H,

2

H₄), ꢃ

1H, H_H). ³¹P{¹H}-NMR (202.3 MHz, C₆D₆, 25 8C): d

172.90 (d, ²J(PP)ꢂ41.4 Hz, 1P, P₁), 79.25 (d, ²J(PP)ꢂ

41.4 Hz, 1P, P₂). The NMR data shows a 10:1 ratio

of RuTp(DPVP)(DMPP)[4ꢀ2]H to RuTp(DPVP)(

DMPP)[4ꢀ

2]Cl. IR (Nujol, cm^ꢃ1): 2468 (w, n(BH)).

/

13.37 (dd, J(HP)ꢂ

/

32 Hz, J(HP)ꢂ

/

26.5 Hz,

1

Et₂O. H-NMR(499.8 MHz, CDCl₃, 25 8C): d 8.44 (m,

/

3

2H, H_o), 8.17 (d, J(HH)ꢂ

/

2.0 Hz, 1H, H_a1), 7.78 (d,

³J(HH)ꢂ

1H, H_g3), 7.49 (d, J(HH)ꢂ

/

2.5 Hz, 1H, H_g1), 7.53 (d, J(HH)ꢂ

/

2.5 Hz,

2.5 Hz, 1H, H_g2), 7.42 (m,

2.5 Hz, 1H, H_a2), 7.22 (m,

3

/

3

/

3

4H, H_m), 7.32 (d, J(HH)ꢂ

/

M.p.: 280 8C dec.

1H, H), 7.19 (m, 2H, H), 7.03 (m, 6H, H_o,m), 6.55 (d,

³J(HH)ꢂ

3

/

2.0 Hz, 1H, H_a3), 6.21 (dd, J(HH)ꢂ2.5, 2.0

/

Hz, 1H, H_b1), 5.83 (dd, ³J(HH)ꢂ

/

2.5, 2.0 Hz, 1H, H_b2),

2.5, 2.0 Hz, 1H, H_b3), 3.57 (bs, 1H,

4.2.11. [(Tp)Ru(DPVP)₂(CH₃CN)]PF₆(12)

3

5.61 (dd, J(HH)ꢂ

/

3

H₅), 3.41 (bs, 1H, H₁), 3.29 (ddd, J(PH)ꢂ

/

20.5 Hz,

2.0 Hz, 1H, H₃), 3.13

²J(H₃H₄)ꢂ

(app dt, ³J(PH)ꢂ

/

12.5 Hz, J(H₃H₅)ꢂ

/

3

/

27.0 Hz, ²J(PH)ꢂ³

/

J(H₂H₄)ꢂ

Hz, 1H, H₂), 1.82 (s, 3H, CH₃), 1.72 (s, 3H, CH³),

1.49 (dddd, ³J(PH)ꢂ29.0 Hz, ³J(PH)ꢂ

12.8 Hz,

²J(H₃H₄)ꢂ12.5 Hz, ³J(H₂H₄)ꢂ

8.8 Hz, 1H, H₄).

³¹P{¹H}-NMR (202.3 MHz, CDCl₃, 25 8C): d 168.01

/

8.8

/

2

(d, J(PP)ꢂ

/

35.0 Hz, 1P, P₁), 50.40 (d, J(PP)ꢂ35.0

/

Hz, 1P, P₂). ¹³C{¹H}-NMR (125.7 MHz, CDCl₃, 25 8C):

d 146.11 (s, C_a3), 144.54 (s, C_a1), 143.68 (s, C_a2), 138.78

2

1

(d, J(PC)ꢂ

/

1.9 Hz, C₆), 135.88 (d, J(PC)ꢂ

/

33.3 Hz,

(Tp)Ru(DPVP)₂Cl, 10, (510 mg, 0.659 mmol) and

NH₄PF₆(122 mg, 0.749 mmol) were dissolved in

CH₂Cl₂(15 ml) and acetonitrile was added (10 ml).

The mixture was heated at reflux under nitrogen over-

night. The resulting precipitate (NH₄Cl) was removed

by filtration. Ether was added to the filtrate, which

caused the product to precipitate. This was collected on

a glass frit, washed with ether, and dried in vacuum.

Yield: 351.0 mg (83.7%). Anal. Calc. for

C₃₉H₃₉BF₆N₇P₃Ru: C, 50.50; H, 4.24. Found: C,

1

C_i), 135.26 (s, C_g2), 135.43 (d, J(PC)ꢂ

/

32.7 Hz, C_i),

2

135.30 (s, C₅), 135.02 (d, J(PC)ꢂ

/

9.3 Hz, C_o), 135.02

(s, C_g1), 134.46 (s, C_g3), 133.32 (d, ⁴J(PC)ꢂ

/

2.0 Hz, C_p),

25.9 Hz, C_i), 131.64 (d, ²J(PC)ꢂ

8.3

Hz, C_o), 129.43 (d, ⁴J(PC)ꢂ

2.0 Hz, C_p), 128.80 (d,

³J(PC)ꢂ11.3 Hz, C_m), 128.34 (d, ¹J(PC)ꢂ

14.1 Hz,

C_o), 127.97 (d, ³J(PC)ꢂ

8.9 Hz, C_m), 127.38 (d,

³J(PC)ꢂ

8.0 Hz, C_m), 105.47 (s, C_b1), 104.48 (s,

⁵J(PC)ꢂC_b2), 104.15 (s, C_b3), 56.23 (dd, ¹J(PC)ꢂ

132.05 (d, ¹J(PC)ꢂ

/

D.C. Wilson, J.H. Nelson / Journal of Organometallic Chemistry 682 (2003) 272ꢁ

/

289

285

50.23; H, 4.17. ¹H-NMR (499.8 MHz d, CDCl₃, 25 8C):

8.02 (d, 1H, Jꢂ 2.5 Hz, H_g?), 7.68 (d, 2H, Jꢂ2.5 Hz,

H_g), 7.49 (m, 7H, H_a?ꢀH_mꢀH_p), 7.21 (m, 6H, H_oꢀ

H_p), 6.99 (d, 2H, Jꢂ2.5 Hz, H_a), 6.97 (m, 4H, H_m),

6.76 (m, 2H, H_a), 6.39 (apparent t, 4H, Jꢂ9.0 Hz, H_o),

6.15 (apparent t, 1H, Jꢂ2.5 Hz, H_b?), 6.03 (m, 2H, H_b),

5.89 (apparent t, 2H, Jꢂ2.0 Hz, H_b), 4.94 (m, 2H, H_c),

1.75 (s, 3H, NCCH₃). ³¹P{¹H}-NMR (202.3 MHz d,

CDCl₃, 25 8C): 35.31 (s, 2P, DPVP), ꢃ145.21 (septet,

¹J(PF)ꢂ710 Hz, 1P, PF₆^ꢃ). ¹³C{¹H}-NMR (125.7

MHz d, CDCl₃, 25 8C): 147.02 (s, C_a?), 143.32 (s, C_a),

H_b), 5.70 (td, ³J(H_gH_b)ꢂ³

1.0 Hz, 1H, H_b), 4.39 (apparent dt, ²J(PH)ꢂ³

H₂)ꢂ 2.2 Hz, 1H, H₁), 2.86 (dd,

3.0 Hz, ⁴J(H₁H₃)ꢂ

²J(PH)ꢂ7.0 Hz, ⁴J(H₁H₃)ꢂ

2.2 Hz, 1H, H₃), 2.78

/

J(H_bH_a)ꢂ

/

2.0 Hz, ⁵J(PH)ꢂ

/

J(H₁

/

3

2

3

/

(ddd, J(PH)ꢂ

3.0 Hz, 1H H₂), 2.09 (apparent t, J(PH)ꢂ⁴

1.5 Hz, 3H, CH_3(a)), 1.81 (s, 3H, CH_3(b)), 1.47 (d,

⁴J(PH)ꢂ

1.0 Hz, 3H, CH_3(c)), 1.19 (s, 3H, CH_3(d)).

³¹P{¹H}-NMR (202.3 MHz d, CD₂Cl₂, 25 8C): 189.92

(d, ²J(PP)ꢂ36.6 Hz, 1P,P₁), 69.31 (d, ²J(PP)ꢂ

36.6 Hz,

1P, P₂). ¹³C{¹H}-NMR (125.7 MHz d, CD₂Cl₂, 25 8C):

152.09 (d, ²J(PC)ꢂ C), 146.62 (d, ³J(PC)ꢂ

12.8 Hz, Cꢀ

2.1 Hz, C_a), 143.77 (s, C_a), 142.78 (s, C_a), 137.94 (s, Cꢀ

C), 137.32 (s, C_g), 135.87 (dd, ¹J(PC)ꢂ

27.4 Hz,

/

43.5 Hz, J(PH)ꢂ

/

5.0Hz, J(H₁H₂)ꢂ

/

4

/

J(HH)ꢂ

/

1

137.74 (s, C_g?), 135.70 (s, C_g), 133.46 (d, J(PC_a)ꢂ

Hz), 133.43 (dd, [²J(PC_o)ꢀ⁴

J(PC_o)]ꢂ17.5 Hz, C_o),

132.65 (apparent t, [²J(PC_o)ꢀ⁴

J(PC_o)]ꢂ4.0 Hz, C_o),

131.68 (dd, [¹J(PC_i)ꢀ³

J(PC_i)]ꢂ44 Hz, C_i), 130.27 (s,

C_p), 129.94 (s, C_p), 129.34 (dd, [¹J(PC_i)ꢀ³

J(PC_i)]ꢂ46

Hz, C_i), 128.58 (apparent t, [³J(PC_m)ꢀ⁵

J(PC_m)]ꢂ

Hz, C_m), 127.83 (apparent t, [³J(PC_m)ꢀ⁵

J(PC_m)]ꢂ

/

37.7

/

1

/

³J(PC)ꢂ

134.78 (s, C_g), 134.42 (s, Cꢀ

²J(PC)ꢂ

/

3.5 Hz, C_i), 135.57 (d, J(PC)ꢂ

/

29.3 Hz, C_i),

/

C), 134.33 (s, C_g), 132.34 (d,

2

/

15.0

16.5

/

8.5 Hz, C_o), 131.00 (d, J(PC)ꢂ

/

8.5 Hz, C_o),

4

/

130.12 (d, J(PC)ꢂ

/

2.5 Hz, C_p), 128.99 (s, C_b), 128.77

9.2 Hz, C_m), 128.59 (d, J(PC)ꢂ

3

Hz, C_m), 124.35 (s, C_b), 106.59 (s, C_b?), 106.43 (s, C_b),

(d, J(PC)ꢂ

C_m), 124.90 (d, J(PC)ꢂ

104.66 (d, J(PC)ꢂ

13.2 Hz, ²J(PC)ꢂ

/

6.4 Hz,

4

1

3.07 (m, J(PC), NCCH₃). IR (Nujol, cm^ꢃ1): 2486 (m,

/

47.0 Hz, C₃), 105.19 (s, C_b),

3

n_BꢁH), 2281 (w, n_CN). M.p.: 137 8C.

/

2.1 Hz, C_b), 62.08 (dd, J(PC) ꢂ

/

5.4 Hz, C₅), 55.05 (dd, ¹J(PC)ꢂ

11.3 Hz, C₁), 53.02 (dd, ¹J(PC)ꢂ

5.4 Hz, C₆), 52.55 (dd, ¹J(PC)ꢂ

/

2

38.5 Hz, J(PC)ꢂ

/

4.2.12. (Tp)Ru(DMPP)₂[4ꢀ2]Cl (13)

/

21.4 Hz, ³J(PC)ꢂ

/

2

3

32.1 Hz, J(PC)ꢂ

/

28.8 Hz, C₂), 27.14 (d, J(PC)ꢂ4.3

/

3

Hz, CH_{3 (a)}), 18.62 (d, J(PC)ꢂ13.2 Hz, CH_3(d)), 17.61

/

(s, CH_3(c)), 15.99 (s, CH_3(b)). IR (Nujol, cm^ꢃ1): 2478 (m,

n_BꢁH). M.p.: dec. 275 8C.

4.2.13. Reactions with phenylacetylene

Solutions of 10 in CH₃OH containing an excess of

phenylacetylene were heated for 24 h at reflux in the

presence and absence of a stoichiometric quantity of

NH₄PF₆. In both cases 10 was recovered unchanged. A

solution of 12 in CH₂Cl₂ꢁCH₃OH containing an excess

/

DMPP (0.2 ml, 1.06 mmol) was added to a solution of

RuTp(COD)Cl (0.30 g, 0.65 mmol) in DMF (22 ml) and

the orange solution was heated to reflux. As the solution

refluxed it turned from orange to dark red in a period of

5 h at which time the solvent was removed by vacuum

distillation. The reddish-foamy residue was dissolved in

CH₂Cl₂and the insolubles were removed by filtration.

Hexane was added to the filtrate and the solution was

of phenylacetylene was heated at 40 8C overnight, and

12 was recovered unchanged. Solutions of 13 in CH₃OH

containing an excess of phenylacetylene and NH₄PF₆or

AgPF₆were heated at reflux overnight and 13 was

recovered unchanged.

4.2.14. Transfer hydrogenation of acetophenone

The catalyst (0.08 mmol) and 2-propanol (85 ml) were

heated at reflux until dissolved. Then acetophenone (8.5

mmol) and NaⁱOPr (0.14 mmol) were introduced into

the solution. The reaction mixture was heated at reflux

for the required time. Once the reaction was complete

concentrated until a reddishꢁorange solid precipitated.

/

The precipitate was isolated by filtration and placed in a

vacuum oven to dry. Yield 0.1630 g (35%). Anal. Calc.

for C₃₃H₃₆BClN₆P₂Ru: C, 54.45; H, 4.98. Found: C,

54.18: H, 4.79%. ¹H-NMR(499.8 MHz d, CD₂Cl₂,

1

(monitored by H-NMR spectroscopy) the solvent was

removed by rotary evaporation. The remaining liquids

were distilled under reduced pressure.

3

25 8C): 7.87 (m, 4H, H_o), 7.71 (dd, J(H_gH_b)ꢂ

/

2.5 Hz,

2.0

Hz, 1H, H_g), 7.46 (m, 7H, H_m, H_p, H_g), 7.19 (d,

⁴J(H_aH_g)ꢂ

/

1.0 Hz, 1H, H_g), 7.63 (d, ³J(H_gH_b)ꢂ

/

3

³J(H_bH_a)ꢂ

Hz, 1H, H_a), 6.37 (d, J(H_bH_a)ꢂ

/

1.5 Hz, 1H, H_a), 6.62 (d, J(H_bH_a)ꢂ

/

2.0

4.2.15. [(Tpm(Ru(DPVP)₂Cl]PF₆(14)

A

3

/

2.0 Hz, 1H, H_a), 6.15

mixture containing [(Tpm)Ru(COD)Cl]PF₆

3

(dd, J(H_gH_b)ꢂ

5.91 (dq, ²J(PH)ꢂ

5.89 (apparent t, ³J(H_gH_b)ꢂ³

/

2.5 Hz, J(H_bH_a)ꢂ

28.5 Hz, ⁴J(HH)ꢂ

J(H_bH_a)ꢂ

/

2.0 Hz, 1H, H_b),

1.5 Hz, 1H, H_a?),

2.0 Hz, 1H,

(0.301g, 0.500 mmol) and diphenylvinylphosphine,

DPVP, (0.20ml, 1.00 mmol) in DMF (25 ml) was heated

at reflux under an atmosphere of nitrogen overnight.

/

286

D.C. Wilson, J.H. Nelson / Journal of Organometallic Chemistry 682 (2003) 272ꢁ289

/

The solvent was removed in vacuo leaving a yellow solid

of 14. Yield 0.1723g (35%). Anal. Calc. for

C₃₈H₃₆ClF₆N₆P₃Ru: C, 54.59; H, 4.34. Found: C,

54.36; H, 4.51%. X-ray quality crystals were obtained

by the diffusion of ether into an acetone solution of 14.

¹H-NMR (499.8 MHz, d, acetone-d₆, 25 8C): 9.45 (s,

2.5 Hz, 2H, H_b), 5.67 (dd, ³J(H_b?H_g?)ꢂ

3.0 Hz,

/

³J(H_b?H_a?)ꢂ

/

2.0 Hz, 1H, H_b?), 5.47 (d, 3J(H_a?H_b?)ꢂ

/

2.0 Hz, 1H, H_a?), 3.24 M (4H, 2CH₂). ¹³C{¹H}-NMR

(125.7 MHz, acetone-d₆, 25 8C): d 151.25 (s, 2C, C_a),

2

147.08 (s, 1C, C_a?), 136.47 (AXX?, J(PP)ꢂ

/

19.9 Hz,

3

¹J(PC)ꢂ

/

ꢃ

/

1.74 Hz, J(PC)ꢂ

/

39.9 Hz, 2C, C_i), 135.79

1H, HCN₃), 8.66 (d, ³J(H_g?H_b?)ꢂ

/

2.5 Hz, 1H, H_g?), 8.42

(s, 1C, C_g?), 135.06 (s, 2C, C_g), 133.91 (t,

[²J(PC)ꢀ⁴

J(PC)]ꢂ8.3 Hz, 4C, C_o), 133.12 (t,

[²J(PC)ꢀ⁴

J(PC)ꢂ8.5 Hz, 4C, C_o), 131.51 (AXX?,

²J(PP)ꢂ19.9 Hz, ¹J(PC)ꢂ43.4 Hz, ³J(PC)ꢂ

2.1

Hz, 2C, C_i), 131.13 (s, 2C, C_p), 130.53 (s, 2C, C_p),

129.52 (t, [³J(PC)ꢀ⁵

J(PC)]ꢂ8.9 Hz, 4C, C_m), 128.74 (t,

[³J(PC)ꢀ⁵

J(PC)]ꢂ9.2 Hz, 4C, C_m), 109.27 (s, 1C, C_b?),

108.02 (s, 2C, C_b), 77.70 (s, 1C, HCN₃), 29.92 (m,

[¹J(PC)ꢀ³43.7 Hz, 2C, CH₂). ³¹P{¹H}-NMR

J(PC)]ꢂ

(202.3 MHz, acetone-d₆, 25 8C): d 70.40 (s, 2P, dppe),

3

(d, J(H_gH_b)ꢂ

/

2.5 Hz, 2H, H_g), 7.68 (m,4H, H_o), 7.50

/

(m, 2H, H_p), 7.35 (m, 4H, H_m), 7.34 (d, ³J(H_aH_b)ꢂ

/2.0

/

Hz, 2H, H_a), 7.30 (m, 2H, H_p), 7.23 (d, ³J(H_a?H_b?)ꢂ

/2.0

/

ꢃ

/

Hz, 1H, H_a?), 7.09 (m, 4H, H_m), 6.91 (ddd, ²J(H_aP)ꢂ

/

26

16.2 Hz, 2H, H_a),

6.77 (m, 4H, H_o), 6.35 (apparent t, ³J(H_b?H_g?)ꢂ

2.5 Hz,

³J(H_b?H_a?)ꢂ

3.0 Hz, 1H, H_b?), 6.22 (apparent t,

³J(H_bH_g)ꢂ

2.5 Hz, J(H_bHa)ꢂ

(ddd, ³J(H_bP)ꢂ33.5 Hz, ³J(H_bH_a)ꢂ

²J(H_bH_c)ꢂ

1.5 Hz, 2H, H_b), 5.19 (ddd, J(H_cP)ꢂ

3

Hz, J(H_aH_b)ꢂ

/

12 Hz, J(H_aH_c)ꢂ

/

3

/

2.5 Hz, 2H, H_b), 6.04

/

12.5 Hz,

3

1

/

18.0

ꢃ

/

143.54 (sept, J(PF)ꢂ

708 Hz, 1P, PF₆^ꢃ).

/

3

2

Hz, J(H_cH_a)ꢂ

/

17.5 Hz, J(H_cH_b)ꢂ

/

1.0 Hz, 2H, H_c).

¹³C {¹H}-NMR (125.7 MHz, d, acetone-d₆, 25 8C):

151.58 (s, 1C, C_a?) 148.33 (s, 2C, C_a), 132.25 (s, 1C,

4.2.17. [(Tpm)Ru(DMPP)₂[4ꢀ2]Cl]PF₆(16)

/

C_g?), 135.99 (t, [²J(PC)ꢀ⁴

/

J(PC)]ꢂ

135.12 (s, 2C, C_g), 134.97 (5 lines AXX?, ¹J(PC_a)ꢂ

Hz, ³J(PC)ꢂ 5.8 Hz, ²J(PP)ꢂ

32.1 Hz, C_a), 134.11 (t,

[²J(PC)ꢀ⁴

J(PC)]ꢂ8.9 Hz, 4H, C_o), 133.26 (5 lines

AXX’, J(PC)ꢂ43.9 Hz, J(PC)ꢂ

32.1 Hz, 2C, C_i), 132.30 (5 lines AXX’, J(PC)ꢂ

Hz, ³J(PC)ꢂ 5.5 Hz, ²J(PP)ꢂ

32.1 Hz, 2C, C_i),

131.23 (s, 1C, C_p), 130.69 (s, 1C, C_p), 130.65 (s, 2C,

C_b), 129.02 (t, [³J(PC)ꢀ⁵

J(PC)]ꢂ9.2 Hz, C_m), 128.85

(t, [³J(PC)ꢀ⁵

J(PC)]ꢂ9.4 Hz, C_m), 109.02 (s, C₂),

108.99 (s, C₂?), 76.51 (s, HCN₃). ³¹P{¹H}-NMR (202.3

MHz, acetone-d₆, 25 8C): d 35.7 (s, 2P, DPVP), ꢃ145.0

/8.9 Hz, 4H, C_o),

/

28.6

/

ꢃ

/

1

3

2

/

ꢃ

/

.8 Hz, J(PP)ꢂ

/

1

/

49.7

/

ꢃ

/

A solution containing [(Tpm)Ru(COD)Cl]PF₆(0.651

g, 1.08 mmol) and 3,4-dimethyl-1-phenylphosphole,

DMPP, (0.3 ml, 1.60 mmol) in DMF (35 ml) was heated

at reflux under nitrogen for 27 h. The solvent was

removed in vacuo to leave an orange glassy residue. The

residue was dissolved in a minimum amount of CH₂Cl₂

and the insolubles were removed by filtration. Ether was

added to the filtrate and the resulting yellow solid was

isolated by filtration to obtain 16. Yield 0.405g (43.1%).

Anal. Calc. for C₃₄H₃₆ClF₆N₆P₃Ru: C, 46.82; H, 4.16.

Found: C, 46.91; H, 4.35%.¹H-NMR (499.8 MHz,

acetone-d₆, 25 8C): d 9.48 (s, 1H, HCN₃), 8.48 (d,

1

(sept, J(PF)ꢂ

/

708 Hz, 1P, PF₆^ꢃ).

4.2.16. [(Tpm)Ru(dppe)Cl]PF₆(15)

A solution containing [(Tpm)Ru(COD)Cl]PF₆(0.204

g, 0.337 mmol) and 1,2-bis(diphenylphosphino)ethane,

dppe, (0.144 g, 0.361 mmol) in DMF (15 ml) was heated

at reflux overnight. The yellow homogeneous solution

turned to a dark brown during the course of the

reaction. The solvent was removed by vacuum distilla-

tion to obtain a green residue. The residue was dissolved

in a minimum amount of CH₂Cl₂and run through a

silica gel/celite column with CH₂Cl₂. Ether was added to

the yellow eluate and the resulting yellow solid was

isolated by filtration to obtain 15. X-ray quality crystals

were obtained by the slow diffusion of ether into an

acetone solution of 15. Yield: 0.969 g (30.9%). Anal.

Calc. for C₃₆H₃₄ClF₆N₆P₃Ru: C, 50.36; H, 3.99. Found:

³J(H_gH_b)ꢂ

Hz, 1H, H_g), 8.23 (d, J(H_gH_b)ꢂ

(m, 4H, H_o), 7.67 (d, 3J(H_aH_b)ꢂ

/

2.0 Hz, 1H, H_g), 8.39 (d, ³J(H_gH_b)ꢂ

/

2.0

3

/

2.0 Hz, 1H, H_g), 7.97

/

2.0 Hz, 1H, H_a), 7.59

3

(m, 2H, H_p), 7.52 (m, 4H, H_m), 6.83 (d, J(H_aH_b)ꢂ

/

2.0

3

Hz, 1H, H_a), 6.59 (t, J(H_bH_g)ꢂ³

/

J(H_bH_a)ꢂ

/

2.0 Hz,

3

1H, H_b), 6.52 (d, J(H_aH_b)ꢂ

/

2.0 Hz, 1H, H_a), 6.33 (t,

2.0 Hz, 1H, H_b), 6.19 (dq,

29.5 Hz, J(HH)ꢂ1.5 Hz, 1H, H_a?), 6.11 (t,

³J(H_bH_g)ꢂ³

J(H_bH_a)ꢂ2.0 Hz, 1H, H_b), 4.38 (app dt,

²J(PH)ꢂ³3.5 Hz, ⁴J(H₁H₃)ꢂ

J(H₁H₂)ꢂ 2.2 Hz, 1H,

H₁), 3.45 (app t, J(PH)ꢂ⁴

J(H₁H₃)ꢂ2.2 Hz, 1H, H₃),

2.94 (ddd, ³J(PH)ꢂ44.0 Hz, ²J(PH)ꢂ

5.5 Hz,

³J(H₁H₂)ꢂ

3.5 Hz, 1H, H₂), 2.24 (app t,

1

C, 50.19; H, 4.08%. H-NMR (499.8 MHz, acetone-d₆,

³J(H_bH_g)ꢂ³

²J(PH)ꢂ

/

J(H_bH_a)ꢂ

/

3

4

25 8C): d 9.64 (s, 1H, HCN₃), 8.53 (d, J(H_gH_b)ꢂ

/

2.5

3.0 Hz,

0.5 Hz, 1H, H_g?), 7.67 (m, 4H, H_o), 7.50

(d, J(H_aH_b)ꢂ2.5 Hz, 2H, H_a), 7.45 (m, 2H, H_p), 7.40

(m, 4H, H_m), 7.30 (m, 2H, H_p), 7.13 (m, 4H, H_m), 6.93

/

Hz, 2H, H_g), 8.33 (dd, ³J(H_g?H_b?)ꢂ

/

⁴J(H_g?H_a?)ꢂ

/

3

2

/

(m, 4H, H_o), 6.53 (apparent t, J(H_bH_g)ꢂ³

/

J(H_bH_a)ꢂ

/

3

D.C. Wilson, J.H. Nelson / Journal of Organometallic Chemistry 682 (2003) 272ꢁ

/

289

287

⁴J(PH)ꢂ⁴

CH₃(c)), 1.55 (s, 3H, CH₃(d)), 1.28 (s, CH₃(a)).

/

J(HH)ꢂ

/

1.5 Hz, 3H, CH₃(b)), 1.83 (s, 3H,

[¹J(PC)ꢀ²

2479 (m, n(Bꢁ

/

J(PC)]ꢂ

/

10.2 Hz, CH₂). IR (Nujol, cm^ꢃ1):

/

H)), 1652 (m, n(CO)). M.p.: 172 8C, dec.

¹³C{¹H}-NMR (125.8 MHz, acetone-d₆), 25 8C): d

2

154.72 (d, J(PC)ꢂ

/

13.3 Hz, CꢀC), 150.38 (s, 1C, C_a),

/

4.3. X-ray data collection and processing

146.41 (s, 1C, C_a), 145.50 (s, 1C, C_a), 138.91 (d,

²J(PC)ꢂ

1.3 Hz, CꢀC), 137.12 (s, 1C, C_g), 134.91 (dd,

¹J(PC)ꢂ

1C, CꢀC), 133.69 (s, 1C, C_g), 132.84 (d, J(PC)ꢂ

Hz, 2C, C_o), 131.40 (d, ²J(PC)ꢂ

8.8 Hz, 2C, C_o), 131.34

/

Crystals of 2 and 4 (acetonitrile); 6, 10, 11 and 13

3

/

32.9 Hz, J(PC)ꢂ

/

2.9 Hz, 1C, C_i), 134.58 (d,

(CH₂Cl₂ꢁ

/

ether); 8 (CH₃NO₂ꢁ/ether); 14, 15 and 17

/

14.8 Hz, 1C, C_i), 134.32 (s, 1C, C_g), 133.96 (s,

(acetoneꢁ/ether) were mounted on glass fibers, coated

2

/

8.9

with epoxy, and placed on a Siemens P4 diffractometer.

Intensity data were taken in the v-mode at 298 K with

/

4

(d, J(PC)ꢂ

Hz, 1C, C_b), 129.47 (d, ³J(PC)ꢂ

129.29 (d, ³J(PC)ꢂ

8.5 Hz, 2C, C_m), 123.77 (d,

¹J(PC)ꢂ

50.3 Hz, C₃), 108.66 (d, J(PC)ꢂ

C_b), 108.15 (d, J(PC)ꢂ

/

2.6 Hz, 1C, C_p), 130.27 (d, J(PC)ꢂ

/1.1

Moꢁ

0.71073 A). Three check reflections monitored every

100 reflections showed random (B2%) variation during

/

K_agraphite monochromated radiation (lꢂ

/

˚

/

9.7 Hz, 2C, C_m),

/

4

/

1.1 Hz, 1C,

the data collections. The data were corrected for

Lorentz, polarization effects and absorption using an

emperical model derived from azimuthal data collec-

tions. Scattering factors and corrections for anomalous

dispersion were taken from a standard source [80].

Calculations were performed with the ^SHELXTLplus

version 5.10 software package on a personal computer.

The structures were solved by Patterson methods.

Anisotropic thermal parameters were assigned to all

non-hydrogen atoms. Hydrogen atoms were refined at

4

/

2.4 Hz, 1C, C_b), 77.47 (s, 1C,

2

HCN₃), 62.59 (dd, J(PC)ꢂ

/

13.4 Hz, J(PC)ꢂ

/

5.9 Hz,

10.8 Hz,

24.0 Hz, J(PC)ꢂ5.2 Hz,

32.8 Hz, ²J(PC)ꢂ

29.2 Hz,

5.0 Hz, 1C, CH₃(a)), 18.42

1C, C₅), 55.42 (dd, ¹J(PC)ꢂ

/

39.8 Hz, ²J(PC)ꢂ

/

1

3

1C, C₁), 52.42 (dd, J(PC)ꢂ

/

1C, C₆), 52.11 (dd, ¹J(PC)ꢂ

/

3

1C, C₂), 26.94 (d, J(PC)ꢂ

(d, J(PC)ꢂ

/

2

3

/

13.8 Hz, 1C, CH₃(b)), 17.49 (d, J(PC)ꢂ

/

1.4 Hz, 1C, CH₃(c)), 15.70 (s, 1C, CH₃(d)). ³¹P{¹H}-

NMR (202.3 MHz, acetone-d₆, 25 8C): d 187.38 (d,

2

²J(PP)ꢂ

1P, P₂), ꢃ

/

37.2 Hz, 1P, P₁), 72.47 (d, J(PP)ꢂ

/

37.2 Hz,

calculated positions with a riding model in which the Cꢁ

/

1

143.58 (sept, J(PF)ꢂ

708 Hz), 1P, PF₆^ꢃ).

/

˚

H vector was fixed at 0.96 A.

/

4.2.18. [(Tp)Ru(dppe)(Me₂CO)]PF₆(17)

5. Supplementary material

A heterogeneous yellow suspension of (Tp)Ru(dp-

pe)Cl (0.394 g, 0.527 mmol) and AgPF₆(0.170g, 0.672

mmol) in acetone (30 ml) was heated to a gentle reflux

overnight. The solution was then cooled to r.t. and

filtered over Celite to remove AgCl and excess AgPF₆.

The solvent was removed from the filtrate and a yellow

solid remained. Yield 0.346 g (70.1%). X-ray quality

crystals were obtained by slow diffusion of ether into an

acetone solution of the product. The crystals were red in

color. Anal. Calc. for C₃₈H₄₀BF₆N₆OP₃Ru: C, 49.85; H,

Crystallographic data for the structural analyses have

been deposited with the Cambridge Crystallographic

Data Centre, CCDC no. 210294ꢁ210303 for compounds

/

2, 4, 6, 8, 10, 11, 13, 14, 15 and 17, respectively. Copies

of this information may be obtained free of charge from

The Director, CCDC, 12 Union Road, Cambridge CB2

1EZ, UK (Fax:

it@ccdc.cam.ac.uk or www: http://www.ccdc.cam.

ꢀ44-1223-336033; e-mail: depos-

/

ac.uk).

4.40. Found: C, 49.57; H, 4.12%. ¹H-NMR (499.8 MHz

3

d, CD₃NO₂, 25 8C): 8.05 (d, J(H_gH_b)ꢂ

/2.0 Hz, 2H,

H_g), 8.80 (d, ³J(H_g?H_b?)ꢂ

H_oꢀH_m), 7.31 (m, 2H, H_p), 7.10 (m, 4H, H_m), 6.98 (d,

³J(H_bH_a)ꢂ

Hz, 1H, H_a?) 6.85 (m, 2H, H_p), 6.81 (m, 4H, H_o), 6.25 (t,

³J(H_gH_b)ꢂ

2.0 Hz, 2H, H_b), 6.21 (apparent t,

³J(H_g?H_b?)ꢂ³

J(H_b?H_a?)ꢂ2.0 Hz, H_b?), 3.43 (m, 4H, 2

CH₂), 2.07 (s, 6H, 2 CH₃). ³¹P{¹H}-NMR (202.3 MHz

d, CD₃NO₂, 25 8C): 72.81 (2p, dppe), ꢃ145.0 (septet,

¹J(PF)ꢂ707 Hz, 1P, PF₆^ꢃ). ¹³C{¹H}-NMR (125.7

MHz d, CD₃NO₂, 25 8C): 143.71 (s, C_a?), 136.46 (s,

C_a), 136.03 (s, C_g?), 132.74 (T, [²J(PC)ꢀ⁴

J(PC)]ꢂ9.4

Hz, C_o), 131.60 (T, [²J(PC)ꢀ⁴

J(PC)]ꢂ9.0 Hz, C_o),

130.63 (s, C_p), 130.30 (s, C_p), 129.03 (T,

[³J(PC)ꢀ⁵

J(PC)]ꢂ8.7 Hz, C_m), 128.40 (T,

[³J(PC)ꢀ⁵

J(PC)]ꢂ9.8 Hz, C_m), 106.18 (s, C_b?), 105.76

(C_b?), 29.38 (s, OC(CH₃)₂), 29.18 (AXX?,

/

2.0 Hz, 1H, H_g?), 7.47 (m, 8H,

Acknowledgements

/

3

/

2.0 Hz, 2H, H_a), 6.95 (d, J(H_aH_b)ꢂ2.0

/

This research was supported by an award from the

Research Corporation and by the donors of the

Petroleum Research Fund Administered by the Amer-

ican Chemical Society. We are grateful for this support.

/

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Reactions of ruthenium(II) tris(pyrazolyl)borate and tris(pyrazolyl) methane complexes with diphenylvinylphosphine and 3,4-dimethyl-1-phenylphosphole

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