Molybdenum tetracarbonyl complexes with functionalised aminophosphine ligands: cis-[Mo(CO)4(PPh2NHR)2] (R = Ph, But) - Molecular structures of PMes2NHPh (Mes = 2,4,6-Me3C6H2

Article abstract of DOI:10.1016/S0277-5387(00)00599-4

The aminophosphines PPh₂NHR [R = Ph (1a), Bu^t (1b)] react readily with cis-[Mo(CO)₄(NCEt)₂] to give cis-[Mo(CO)₄(PPh₂NHR)₂] [R = Ph (2), Bu^t (3)] in high yield, while

Full text of DOI:10.1016/S0277-5387(00)00599-4

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Polyhedron 20 (2001) 111–117
Molybdenum tetracarbonyl complexes with functionalised
aminophosphine ligands: cis-[Mo(CO)4(PPh2NHR)2] (R=Ph,
But) — molecular structures of PMes2NHPh
(Mes=2,4,6-Me3C6H2), PPh2NHBut and
cis-[Mo(CO)4(PPh2NHBut)2]
Olaf Ku¨hl, Steffen Blaurock, Joachim Sieler, Evamarie Hey-Hawkins *
Institut fu¨r Anorganische Chemie, Uni6ersita¨t Leipzig, Johannisallee 29, D-04103 Leipzig, Germany
Received 24 July 2000; accepted 28 September 2000
Abstract
The aminophosphines PPh2NHR [R=Ph (1a), But (1b)] react readily with cis-[Mo(CO)4(NCEt)2] to give cis-
[Mo(CO)4(PPh2NHR)2] [R=Ph (2), But (3)] in high yield, while the bulky aminophosphine PMes2NHPh (1c) (Mes=2,4,6-
Me3C6H2), obtained from LiNHPh and PMes2Cl, does not react even at elevated temperature. Compounds 1c, 2 and 3 were
1
characterised spectroscopically (IR; H, 31P, 13C NMR), 2 and 3 also by MS, and crystal structure determinations were carried
out on 1b, 1c and 3; for 3, this showed the presence of the cis isomer. Complexes 2 and 3 do not react with [Cp2ZrCl2]/NEt3 or
with [Cp2ZrMe2]. © 2001 Elsevier Science B.V. All rights reserved.
Keywords: Molybdenum; Aminophosphine ligands; cis Isomers; Molecular structures
1. Introduction
methylalumoxane (MAO) [7]. In our investigations on
phosphinoamides and -amines as potential mono- and
bidentate ligands in transition metal complexes, we
have also obtained the Ni(0) complex [Ni(PPh2NHPh)4]
[8] with bulky phosphinoamine ligands. We now report
the synthesis of the molybdenum carbonyl complexes
cis-[Mo(CO)4(PPh2NHR)2] [R=Ph (2), But (3)] in high
yield.
While numerous mononuclear and heterodinuclear
molybdenum(0) tetracarbonyl complexes with cis-coor-
dinated phosphine ligands have been structurally char-
acterised [9], the number of corresponding compounds
with bifunctional phosphine ligands, such as phosphi-
noamine ligands [3], is still rather small. Only a few
examples for structurally characterised heterodinuclear
complexes in which Mo and M% (M%=Ni [4a,b], Cu
[4c]) are bridged by P,N ligands have been reported. As
molybdenum bis(diphosphine) complexes also have cat-
alytic potential [10], the use of mixed soft–hard P,N
ligands in the preparation of heterodinuclear molyb-
denum complexes appears attractive, as early–late
While tertiary phosphines have long been employed
as ligands in the synthesis of transition metal complexes
with catalytic properties [1], secondary phosphi-
noamines have received only limited attention [2,3], and
only a few examples of heterodinuclear complexes in
which a phosphinoamido or -amine ligand bridges two
different metals have been reported to date [4]. Several
transition metal [2d,e,5] and lanthanide complexes [6]
with phosphinoamido ligands are known in which the
anionic ligand can be terminal, chelating or bridging.
Some of them have been employed in transition metal
catalysed synthesis [2c]. Recently, we have shown that
the
homoleptic
phosphinoamide
complex
[Zr(NPhPPh2)4] and the related bisamido complex
[TiCl2{N(PPh2)2}2] are active catalysts for the forma-
tion of elastomeric polypropylene in the presence of
* Corresponding author. Tel.: +49-341-973-6151; fax: +49-341-
973-9319.
E-mail address: hey@rz.uni-leipzig.de (E. Hey-Hawkins).
0277-5387/01/$ - see front matter © 2001 Elsevier Science B.V. All rights reserved.
PII: S0277-5387(00)00599-4

112
O. Ku¨hl et al. / Polyhedron 20 (2001) 111–117
bridged transition metal complexes may show coopera-
tive reactivity in catalytic processes, which stems from
the possibility for the electron-poor early transition
metal and the electron-rich late transition metal to
create an ideal environment for heterolytic bond cleav-
age of polar substrates.
Me3C6H2 (Mes)] to give aminophosphines PPh2NHR
(R=Ph (1a) [11], But (1b) [12]) and PMes2NHPh (1c);
Eq. (1)).
LiNHR+PR%Cl“PR%NHR+LiCl
(1)
2
2
The PꢀN bond in aminophosphines is essentially a
single bond [6,13], so the lone pairs on nitrogen and
phosphorus are available for donor bonding towards
metal atoms.
2. Synthesis and spectroscopic properties of
phosphinoamines
In the 1H NMR spectra, the NꢀH signals were
observed as doublets at 4.38 ppm (2JPH=7.8 Hz) for 1a
[14], 1.96 ppm (2JPH=11.6 Hz) for 1b [12,15], and 4.34
ppm (2JPH=9.0 Hz) for 1c. The 31P{1H} NMR spectra
of the aminophosphines in CDCl3 show singlets at 28.6
Lithium amides LiNHR (R=Ph, But) react readily
with diarylchlorophosphines PR%Cl [R%=Ph, 2,4,6-
2
2
ppm (1a), 22.5 ppm (1b), and 19.4 ppm (1c). No JPH
coupling was observed in the 31P NMR spectra. The
chemical shifts in the 31P{1H} NMR spectra are in
accordance with the electronic properties of the sub-
stituents on nitrogen and phosphorus. Thus, substitu-
tion of mesityl for phenyl on phosphorus results in the
expected high-field shift of 1c (Dl=9.2 ppm) due to the
increased electron density on phosphorus. The same
effect, but to a higher degree, is observed when the
Mes* substituent (Mes*=2,4,6-But3C6H2, 48.6 ppm
[13]) on nitrogen is substituted for phenyl (28.6 ppm) or
But (22.5 ppm). 1,2-Bis(diphenylphosphinoamino)-
benzene (32.5 ppm) and 3,4-bis(diphenylphosphi-
noamino)toluene (33.3, 30.4 ppm) also fit into this
series [3e].
In the IR spectra (KBr), the w(NH) band is observed
at 3295 cm−1 (1a), 3400 cm−1 (1b) [12], and 3364
cm−1 (1c). The w(PN) vibration is tentatively assigned
to a very strong absorption at 892 cm−1 (1a) and 979
cm−1 (1b). 1,2-Bis(diphenylphosphinoamino)benzene
and 3,4-bis(diphenylphosphinoamino)toluene have
w(NH) bands at 3328 and 3329 cm−1 and w(PN) bands
at 904 and 887 cm−1, respectively [3e].
Fig. 1. Molecular structure of 1b (ORTEP, 50% probability, SHELXTL
PLUS; XP) [26]. Only one of the two independent molecules is shown.
3. Molecular structures of PPh2NHBut (1b) and
PMes2NHPh (1c)
PPh2NHBut (1b) (Fig. 1) crystallises monoclinic in
the space group P21 (no. 4) with two independent
molecules in the asymmetric unit and four molecules in
the unit cell, PMes2NHPh (1c) (Fig. 2) crystallises
monoclinic in the space group P21/c (no. 14) with four
molecules in the unit cell. A comparison of selected
bond lengths and angles in 1b and 1c with those of
related aminophosphines is shown in Table 1.
In both molecules, the phosphorus atom is coordi-
nated in a distorted tetrahedral fashion by a nitrogen
atom, two carbon atoms of the phenyl [C(1), C(7), and
C(17), C(23)] or mesityl [C(7) and C(16)] substituents,
Fig. 2. Molecular structure of 1c (ORTEP, 50% probability, SHELXTL
XP) [26]. Hydrogen atoms (other than NꢀH) omitted for clarity.
PLUS
;

O. Ku¨hl et al. / Polyhedron 20 (2001) 111–117
113
Table 1
Comparison of selected bond lengths and angles in aminophosphines
4. Synthesis and spectroscopic properties of
cis-[Mo(CO)4(PPh2NHR)2] (R=Ph, But)
,
Complex
PꢀN (A) CꢀPꢀN (°)
PꢀNꢀC (°)
The aminophosphines 1a, b react readily with cis-
PPh2NHPh6
1.696(3)
1.730(2)
[Mo(CO)4(NCEt)2]
[16]
to
give
cis-
b
b
PPh2NHMes13
99.7(1), 102.1(1)
114.6(1)
120.9(4),
127.0(4)
126.1(2)
[Mo(CO)4(PPh2NHR)2] (R=Ph (2), But (3)) in high
yield (Scheme 1). Compound 1c does not react even at
elevated temperature, only decomposition of cis-
[Mo(CO)4(NCEt)2] occurs.
PPh2NHBut (1b) a 1.673(5), 101.8(2), 104.9(2)
1.701(5)
1.703(2)
PMes2NHPh (1c)
96.83(9), 108.80(9)
a Two independent molecules.
b No values reported.
Apparently, the greater steric hindrance of the
mesityl substituent in 1c compared with the phenyl
substituent in 1a, b is the reason for this. A similar
behaviour was observed for the organic triphos ligand
CH3C(CH2PR2)3 (R=o-tolyl), in which the o-tolyl
substituent causes a significant decrease in the ligating
strength of the triphos ligand relative to the phenyl-sub-
stituted ligand [17].
In the 31P{1H} NMR spectra, 2 and 3 exhibit singlets
which show the expected low-field shifts relative to the
uncoordinated ligands [2: 70.8 ppm (Dl=42.2 ppm), 3:
69.2 ppm (Dl=46.7 ppm)]. In addition, satellites in-
dicative of an ABX spin system are visible, but at a
resolution too poor to determine the 31P–31P coupling
constant. In the 13C{1H} NMR spectrum of 2 the
pattern of an ABX spin system is clearly visible for the
trans-CO carbon atoms at 214.8 ppm and the ipso-C
atoms of the phenyl rings on phosphorus at 136.8 ppm,
respectively.
The IR spectra of 2 and 3 show the typical pattern
for cis-[Mo(CO)4(phosphine)2] complexes (local symme-
try C26) in the carbonyl region. In these and related
complexes [3,9,18] usually only three of the four ex-
pected absorptions are observed in the range of 1870–
2025 cm−1. In addition, 2 and 3 exhibit a w(NH) band
at 3383 and 3385 cm−1, respectively, which is shifted to
higher wavenumbers for 2 (Dw=85 cm−1), but to lower
wavenumbers for 3 (Dw= −15 cm−1) compared with
1a, b. The w(PN) vibration in 2 and 3 is tentatively
assigned to strong absorptions at 906 cm−1 (2) and
1010 cm−1 (3). In cis-[Mo(CO)4(PPh2NR2)2] (R=Me,
Et, Pr, Bu), the w(PN) band is observed in the same
range (at 926–985 cm−1) [3l].
Scheme 1.
and the electron lone pair. In 1c, two of the three bond
angles between the substituents [N(1)ꢀP(1)ꢀC(16)
108.80(9) and C(16)ꢀP(1)ꢀC(7) 105.17(9)°] are near to
the tetrahedral angle of 109.5°, while the third bond
angle [N(1)ꢀP(1)ꢀC(7) 96.83(9)°] is significantly smaller.
This effect is less pronounced in the less crowded
molecule 1b [NꢀPꢀC 101.8(2)–104.9(2), CꢀPꢀC 98.8(2),
100.5(2)°]. The PꢀC bond lengths of 1.829(5)–1.845(5)
,
(1b) and 1.847(2)–1.853(2) A (1c) and the PꢀN bond
5. Molecular structure of cis-[Mo(CO)4(PPh2NHBut)2]
(3)
,
lengths of 1.673(5), 1.701(5) (1b) and 1.703(2) A (1c) are
in the expected range.
The nitrogen atom in 1b, c has a trigonal-planar
environment formed by H(1N) [or H(2N)], C(13) [or
C(29)] and P(1) [or P(2)] (1b), or H(1), C(1) and P(1)
(1c) (sum of bond angles at N: 359.0, 347.9° for 1b;
359.1° for 1c). In 1b, the PꢀNꢀH [126(6), 126(4)°] and
PꢀNꢀC [120.9(4), 127.0(4)°] angles are larger than the
CꢀNꢀH bond angles [101(7), 106(4)°]. In 1c, the bond
angle C(1)ꢀN(1)ꢀP(1) of 126.1(2)° is slightly larger than
expected. The conformation about the PꢀN bond in 1b
and 1c is staggered.
Cis-[Mo(CO)4(PPh2NHBut)2] (Fig. 3) crystallises
monoclinic in the space group P21 (no. 4) with two
molecules in the unit cell. Selected bond lengths and
angles are given in Table 2.
The molybdenum atom is octahedrally coordinated
by four carbonyl groups and the two phosphorus atoms
of the two cis-oriented aminophosphine ligands. The
PꢀMoꢀP bond angle of 95.44(3)° is slightly larger than
the ideal angle of 90°. The MoꢀP bond lengths in 3 are

114
O. Ku¨hl et al. / Polyhedron 20 (2001) 111–117
6. Attempted formation of heterodinuclear complexes
Several attempts to employ 2 and 3 in the synthesis
of heterobimetallic ligand-bridged dinuclear complexes
were unsuccessful. Thus, cis-[Mo(CO)4(PPh2NHR)2]
(R=Ph, But) does not react with [Cp2ZrCl2] in the
presence of NEt3 as an auxiliary base, and no CH4
elimination occurred when cis-[Mo(CO)4(PPh2NHR)2]
(R=Ph, But) was treated with [Cp2ZrMe2]. Appar-
ently, the acidity of the NꢀH group in coordinated
aminophosphines is too low.
The phosphinoamine PPh2NHPh [11] is readily de-
protonated by BuLi to give LiNPhPPh2 [19]. Two
mesomeric structures can be formulated for these an-
ions in which the negative charge is localised at the N
(phosphinoamide) or P atom (iminophosphide). Ac-
cording to theoretical calculations [20], the phosphi-
noamide structure is dominant. However, while
lithiation of 3 with BuLi was successful, no further
reaction with [Cp2ZrCl2] was observed.
Fig. 3. Molecular structure of 3 (ORTEP, 50% probability, SHELXTL
PLUS
; XP) [26]. Hydrogen atoms (other than NꢀH) omitted for clarity.
similar to those in related complexes (Table 2). Another
general feature is that the MoꢀC bond lengths of the
carbonyl groups trans to the aminophosphine ligands
(trans effect) are slightly shorter [3: Mo(1)ꢀC(2)
,
1.984(4), Mo(1)ꢀC(4) 1.995(4) A] than those of the
7. Experimental
,
other two carbonyl groups [3: MoꢀC 2.048(4) A]. The
phosphorus atoms of the aminophosphines show dis-
torted tetrahedral coordination. Here the NꢀPꢀMo
bond angles are markedly larger than 109.5° [113.0(1)
and 112.4(1)°], and the other bond angles are corre-
spondingly smaller. The smallest bond angle at phos-
phorus is that between the two phenyl substituents
[CꢀPꢀC 102.9(2) and 102.2(2)°]. The nitrogen atom is
coordinated in a trigonal-planar fashion by phospho-
rus, the carbon atom of the But substituent, and a
hydrogen atom. The sum of the bond angles is 358.8°
(N1) and 355.7° (N2). The bond angles between the two
bulky substituents (PꢀNꢀC) are larger (136.8(2) and
133.7(2)°) than the ideal angle of 120°, whereas those
angles involving the hydrogen atom are correspond-
ingly smaller (109–113°). As in [Ni(PPh2NHPh)4] [8],
the overall structure of PPh2NHPh [6] is almost unin-
fluenced by coordination to the Mo atoms.
All experiments were carried out under purified dry
argon. Solvents were dried and freshly distilled under
argon. NMR spectra: Avance DRX 400 (Bruker), stan-
1
dards: H NMR (400.1 MHz): trace amounts of proto-
nated solvent, C6D6, 13C NMR (100.6 MHz): internal
solvent, 31P NMR (161.9 MHz): external 85% H3PO4.
The IR spectra were recorded as KBr mulls on a
Perkin–Elmer FT-IR spectrometer system 2000 in the
range 350–4000 cm−1. The mass spectra were recorded
with a Sektorfeldgera¨t AMD 402 (AMD Intectra
GmbH; EI, 70 eV). The melting points were determined
in sealed capillaries under argon and are uncorrected.
PPh2NHR (R=Ph (1a) [11], But (1b) [12]),
[Mo(CO)4(NCEt)2] [16], LiNHPh [21], PMes2Cl [22],
[Cp2ZrCl2] [23] and [Cp2ZrMe2] [24] were prepared by
literature procedures.
Table 2
,
Selected bond lengths (A) and bond angles (°) in cis-[Mo(CO)4L2] (L=phosphinoamine, L2=3,4-(PPh2NH)2C6H3Me)
L or L2
PPh2NHPh (3)
PPh2NH2 [3b]
PPh(Cl)NHPri [3c]
3,4-(PPh2NH)2C6H3Me [3e]
MoꢀP
PꢀN
MoꢀCax
MoꢀCeq
2.5386(8), 2.5503(8)
1.665(3)
2.048(4), 2.048(4)
1.984(4), 1.995(4)
2.5218(7), 2.5290(7)
1.677(3), 1.682(2)
2.031(3), 2.051(2)
2.002(3), 1.987(3)
2.459(1), 2.463(1)
1.637(2), 1.639(2)
2.035(2), 2.043(3)
1.999(3), 2.013(3)
2.516(2), 2.471(2)
1.688(6), 1.717(6)
a
a
PꢀMoꢀP
MoꢀPꢀN
PꢀMoꢀCtrans
PꢀMoꢀCcis
95.44(3)
90.06(2)
90.5(1)
84.6(1)
113.0(1), 112.4(1)
175.3(1), 178.1(1)
86.4(1)–91.9(1)
111.6(1), 112.0(1)
176.71(8), 178.36(8)
85.8(1)–94.3(1)
116.5(1), 116.9(1)
178.9(1), 179.7(1)
89.6(1)–91.3(1)
113.9(2), 115.6(2)
a
a
a No values reported.

O. Ku¨hl et al. / Polyhedron 20 (2001) 111–117
115
7.1. Preparation of PMes2NHPh (1c)
7.3. Preparation of cis-[Mo(CO)4(PPh2NHBut)2] (3)
At −78°C, 9.23 ml (13.85 mmol) of a 1.5 M BuLi
solution in hexane was added with a dropping funnel to
a solution of 1.45 ml (13.85 mmol) PhNH2 in 30 ml thf.
The solution was slowly warmed to room temperature
(r.t.) and stirred for 1 h. The solution was then trans-
ferred into a dropping funnel and added dropwise to a
solution of 5.4 g (13.85 mmol) Mes2PCl·C6H14 in 50 ml
thf at −78°C. The solution was stirred for 2 h and
then slowly warmed to r.t. The solvent was removed in
vacuo, the off-white residue dissolved in hexane and
LiCl filtered off. After concentration of the hexane
solution, beige crystals of 1c formed. Yield: 4.0 g (80%).
M.p.: 124–126°C.
PPh2NHBut (0.89 g, 3.47 mmol) and 0.55 g (1.73
mmol) [Mo(CO)4(NCEt)2] were stirred in 30 ml CH2Cl2
for 2 h. The solution was then concentrated in vacuo
and the light brown product precipitated by adding 30
ml hexane. Crystals were obtained from the mother
liquor at −20°C. Yield: 1.04 g (83%). M.p.: 117–
120°C.
1H NMR (CDCl3, ppm): 7.34–7.70 (m, 4 H, m-H in
2
Ph), 7.40–7.38 (m, 6 H, o,p-H in Ph), 2.15 (d, JPH
=
20.0 Hz, 2 H, NH), 0.85 (s, 18 H, C(CH3)3). 13C NMR
(CDCl3, ppm): 216.89 (d, 2JPC=8.1 Hz, CO trans to P),
216.80 (d, 2JPC=8.7 Hz, CO trans to P), 210.31 (t,
2JPC=9.9 Hz, CO cis to P), 139.83 (d, JPC=18.2 Hz,
1
1
1H NMR (CDCl3, ppm): 7.21 (m, 3 H, o,p-H in Ph),
ipso-C in Ph), 139.65 (d, JPC=18.0 Hz, ipso-C in Ph),
4
2
2
7.00 (m, 2 H, m-H in Ph), 6.80 (d, JPH=1.9 Hz, 2 H,
132.62 (d, JPC=6.5 Hz, o-C in Ph), 132.55 (d, JPC=
2
C6H2(CH3)3), 4.34 (d, JPH=9.0 Hz, 1 H, NH), 2.30 (s,
6.5 Hz, o-C in Ph), 129.87 (s, p-C in Ph), 128.45 (d,
3
12 H, o-CH3 in Mes), 2.26 (s, 6 H, p-CH3 in Mes).
31P{1H} NMR (CDCl3, ppm): 19.4 (s). IR (KBr,
cm−1): 3364 cm−1 (vst, NH). Elemental analysis:
C24H28NP (361.45 g): C, 79.53 (79.75); H, 7.94 (7.81);
N, 4.01 (3.88); P, 8.65 (8.57).
3JPC=4.3 Hz, m-C in Ph), 128.41 (d, JPC=4.3 Hz,
m-C in Ph), 56.33 (d, 2JPC=6.7 Hz, C(CH3)3), 56.27 (d,
2JPC=6.7 Hz, C(CH3)3), 32.69 (s, C(CH3)3). 31P{1H}
NMR (CDCl3, ppm): 69.2 (s). IR (cm−1): 3385 (m,
NH), 2018 (vst, CO), 1905 (vst, CO), 1872 (vst, CO),
1010 (st, PN).
7.2. Preparation of cis-[Mo(CO)4(PPh2NHPh)2] (2)
MS [m/z, %]: 723 (M+, 0.01), 695 (M+−CO, 0.02),
667 (M+−2 CO, 0.4), 495 [(OC)5Mo(PPh2NButH)+,
2], 467 (M+−PPh2NHBut, 5), 439 (M+−CO−
PPh2NHBut, 1), 411 (M+−2CO−PPh2NHBut, 10),
PPh2NHPh (5.54 g, 20 mmol) and 3.18 g (10 mmol)
[Mo(CO)4(NCEt)2] were stirred in 50 ml CH2Cl2 for 2
h. The solution was concentrated in vacuo, and the
white product was precipitated with 30 ml hexane.
Crystals were obtained from the mother liquor at −
20°C. Yield: 6.55 g (86%). M.p.: 190–191°C.
383
(M+−3CO−PPh2NHBut,
0.5),
355
(Mo(PPh2NButH)+, 25), 257 (PPh2NHBut+, 93), 200
(PPh2NH+, 100), 185 (PPh+2 , 75), and fragmentation
products thereof. Elemental analysis: C36H40MoN2O4P2
(722.58 g): C, 58.76 (59.84); H, 5.61 (5.58); N, 3.65
(3.88); O, 8.95 (8.86); P, 8.65 (8.57).
1H NMR (CDCl3, ppm): 7.56 (br, 8 H, m-H in
3
PꢀPh), 7.34 (t, JHH=5.1 Hz, 12 H, o,p-H in PꢀPh),
3
3
6.76 (t, JHH=7.7, 4 H, m-H in NꢀPh), 6.58 (t, JHH
=
7.3 Hz, 2 H, p-H in NꢀPh), 5.93 (d, 3JHH=8.0 Hz, 4 H,
7.4. Data collection and structure refinement of 1b,c
and 3
o-H in NꢀPh), 4.34 (d, JPH=22.2 Hz, 2 H, NH). 13C
2
NMR (CDCl3, ppm): 214.81 (m, CO trans to P), 209.78
2
2
(t, JPC=9.9 Hz, CO cis to P), 142.51 (t, JPC=5.5 Hz,
ipso-C in NꢀPh), 136.76 (m, ipso-C in PꢀPh), 131.51 (d,
Data were collected on a Siemens CCD (SMART)
diffractometer with monochromated Mo Ka radiation
2JPC=6.2 Hz, o-C in PꢀPh), 131.45 (d, JPC=6.6 Hz,
(u=0.71073 A) (Table 3). All observed reflections were
2
,
o-C in PꢀPh), 130.45 (s, p-C in PꢀPh), 129.26 (d,
used for determination of the unit cell parameters.
Absorption correction with SADABS [25].
3JPC=4.6 Hz, m-C in Ph), 129.21 (d, JPC=4.6 Hz,
3
m-C in Ph), 129.07 (s, m-C in NꢀPh), 120.91 (s, p-C in
The structure of compound 1b could be solved only
in the monoclinic space group P21 (i=90°). The Rint
value for the monoclinic crystal system was 0.04 and
that for the orthorhombic system 0.12. The normal
refinement procedure for the space group P21 gave a
wR2 value of 0.289 with anisotropic temperature factors
for all non-hydrogen atoms. The refinement procedure
for a pseudo-merohedral twin with the matrix 100 0
−10 00−1 and BASF=0.30 gave a better conver-
gence (wR2=0.131 and R1=0.050).
3
NꢀPh), 118.58 (t, JPC=2.6 Hz, o-C in NꢀPh). 31P{1H}
NMR (CDCl3, ppm): 70.84 (s, P), 13C satellites at 70.96
(s), 70.77 (s), 70.60 (s), 70.41 (s). MS [m/z, %]: 514
[(OC)5Mo(PPh2NHPh)+, 3], 486 [(OC)4Mo(PPh2-
NHPh)+, 3], 430 [(OC)2Mo(PPh2NHPh)+, 12], 374
[Mo(PPh2NHPh)+, 24], 277 (PPh2NHPh+, 100), 200
(PPh2NH+, 66), and fragmentation products thereof.
IR (KBr, cm−1): 3383 (m, NH), 2022 (vst, CO), 1929
(vst, CO), 1902 (vst, CO), 906 (st, PN). Elemental
analysis: C40H32MoN2O4P2 (762.58 g): C, 61.31 (63.00);
H, 4.13 (4.23); N, 3.43 (3.67); O, 8.49 (8.39); P, 8.21
(8.12).
Positions of non-hydrogen atoms were located by
using direct methods (SHELXTL PLUS) [26]. Subsequent
least-squares refinement and difference electron density

116
O. Ku¨hl et al. / Polyhedron 20 (2001) 111–117
Table 3
References
Crystal data and structure refinement for 1b, 1c and 3
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1b
1c
3
Formula
Mr
Temperature
(K)
C
16H20NP
C24H28NP
361.45
220(2)
C36H40MoN2O4P2
722.58
220(2)
257.30
213(2)
Crystal system monoclinic
monoclinic
P21/c (no. 14) P21 (no. 4)
monoclinic
Space group
P21 (no. 4)
10.085(2)
9.560(2)
15.650(3)
90
90.00(3)
90
1508.9(5)
4
,
a (A)
13.4020(3)
7.2409(1)
21.4066(2)
90
92.138(1)
90
2075.09(6)
4
1.156
9.7956(1)
20.7138(1)
10.0850(1)
90
115.879(1)
90
1841.08(3)
2
1.303
,
b (A)
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,
c (A)
h (°)
i (°)
k (°)
3
,
V [A ]
Z
zcalcd
(Mg m−3
F(000)
Crystal size
(mm)
1.133
)
552
0.3×0.3×0.2
776
748
0.5×0.4×0.2 0.2×0.4×0.5
Absorption
0.166
0.139
0.481
coefficient
(mm−1
)
2[max (°)
Reflections
collected
Independent
reflections
Rint
2.6–57.6
9864
3.4–56.0
11457
4.0–54.4
9883
6073
4551
5819
0.0438
486
0.0498
0.0447
347
0.0527
0.1241
0.0281
566
0.0273
0.0690
−0.07(3)
Parameters
R (I\2|(I))
wR2 (all data) 0.1316
Absolute
structure
parameter
(Z/z)min
0.331
0.273
0.355
−3
,
(e A
)
)
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