A molybdenum(0) complex of bis(hydroxymethyl)phenylphosphine

Article abstract of DOI:10.1016/S0020-1693(98)00419-8

The thermal reaction of hexacarbonyl molybdenum with bis(hydroxymethyl)phenylphosphine afforded the 1:1 complex Mo(CO)₅[PPh(CH₂OH)₂]. Its solution spectral behavior and solid-state structure have been determined.

Full text of DOI:10.1016/S0020-1693(98)00419-8

Inorganica Chimica Acta 287 (1999) 209–211
Note
A molybdenum(0) complex of bis(hydroxymethyl)phenylphosphine
John C. Kane a, Glenn P.A. Yap b, Arnold L. Rheingold b,1, Edward H. Wong a,*
a Department of Chemistry, Uni6ersity of New Hampshire, Durham, NH 03824, USA
b Department of Chemistry, Uni6ersity of Delaware, Newark, DE 19716, USA
Received 4 August 1998; accepted 30 November 1998
Abstract
The thermal reaction of hexacarbonyl molybdenum with bis(hydroxymethyl)phenylphosphine afforded the 1:1 complex
Mo(CO)5[PPh(CH2OH)2]. Its solution spectral behavior and solid-state structure have been determined. © 1999 Elsevier Science
S.A. All rights reserved.
Keywords: Crystal structures; Molybdenum complexes; Hydroxymethyl-phosphine complexes; Carbonyl complexes
1. Introduction
ately before use. Elemental analyses were performed on
a Perkin-Elmer 2400 elemental analyzer. Proton, 13C,
and 31P NMR spectra were recorded on a JEOL-FX-
90Q spectrometer and a Bruker AM 360 spectrometer.
IR spectra were obtained as KBr pellets using a Nicolet
MX-1 FT-spectrophotometer.
Hydroxymethylphosphines are useful precursors for
a variety of important phosphorus-containing com-
pounds including aminomethylphosphines, phosphorus
heterocycles and polycycles [1]. The hydrophilic hy-
droxyl group can also endow the ligand and its metal
complexes with enhanced water solubility in biphasic
catalysis as well as radiopharmaceutical applications
[2,3]. We report here on the synthesis, spectral and
structural characterization of a pentacarbonyl moly-
bdenum complex of the bis(hydroxymethyl)phenylphos-
phine ligand.
To a flask containing 6.48 g (381 mmol) of ligand
and 10.1 g (381 mmol) of Mo(CO)6 was added 45 ml of
toluene. After 12 h of refluxing, the reaction mixture
turned yellow. Evaporation of volatiles left a tan solid.
Two portions of 50 ml of hot hexane were used to
extract the residue. The extracts were combined and
filtered hot through celite. Upon slow cooling, the
filtrate yielded 8.97 g (221 mmol, 58%) of white crys-
talline complex after filtration and drying. X-ray qual-
ity crystals were obtained by recrystallization from
2. Experimental
1
hexane. IR (cm−1, CO) 2074, 1957, 1922. H NMR
The bis(hydroxymethyl)phenylphosphine ligand was
prepared according to a literature method [4]. Synthetic
work was performed under a nitrogen atmosphere us-
ing standard Schlenk techniques. Solvents were reagent
grade and dried and distilled under nitrogen immedi-
(CDCl3, l) 7.42–7.64 (m, Ph), 4.48–4.63 (ABMX,
2
2
3
CH2, JHH=12.2, JPH=5.2, and JHH=5.5 Hz), and
2.86 (OH, t of t, 3JHH=3JPH=5.5 Hz). 13C NMR
(CDCl3, l) CO: 208.8 (d, 2JPC=21.8 Hz), 204.9 (d,
2JPC=8.7 Hz); aromatics: 130.8 (d, JPC=9.7 Hz), 130.4
(d, JPC=1.9 Hz), 130.3 (d, JPC=35.0 Hz), and 129.3
(d, JPC=9.0 Hz); CH2: 64.2 (d, JPC=20.2 Hz). 31P
NMR (CDCl3, l) 27.9 (s). Anal. Calc. for
C13H11MoO7P: C, 38.45; H, 2.73. Found: C, 38.61; H,
2.70%.
* Corresponding author. Tel.: +1-603-862 1550; fax: +1-603-862
4278.
1 Also corresponding author.
0020-1693/99/$ - see front matter © 1999 Elsevier Science S.A. All rights reserved.
PII: S0020-1693(98)00419-8

210
J.C. Kane et al. / Inorganica Chimica Acta 287 (1999) 209–211
Crystal data collection, and refinement parameters
are given in Table 1. The structure was solved by direct
methods, completed by subsequent Fourier syntheses
and refined by full-matrix least-squares procedures. All
non-hydrogen atoms were refined anisotropically and
hydrogens were calculated and treated as idealized con-
tributions. All software and sources of scattering factors
are from the SHELXTL (5.3) library (G. Sheldrick,
Siemens XRD, Madison, WI).
3. Results and discussion
In refluxing toluene, hexacarbonylmolybdenum and
bis(hydroxymethyl)phenylphosphine afforded a white
microcrystalline product in moderate yield. Elemental
analyses and IR spectroscopy suggested the formation
of Mo(CO)5[PPh(CH2OH)2]. In CDCl3, the NMR spec-
tral data were also consistent with this formulation of
the product. Its 31P{1H} spectrum contained a single
Fig. 1. Structure of one molecule of Mo(CO)5[PPh(CH2OH)2] in the
asymmetric unit.
in the asymmetric unit, with one of these shown in Fig.
1. The coordination geometry around both molybde-
num centers approximates an octahedron with normal
1
˚
resonance at l 27.9. Its H spectrum in CDCl3 featured
the AB portion of an ABMX pattern for the methylene
Mo–P bond lengths of 2.483(2) and 2.498(2) A, respec-
˚
tively. Average equatorial Mo–C bonds (2.03(1) A) are
protons (M=hydroxyl proton, X=phosphorus) and a
only marginally longer than the axial bonds (2.014(8)
and 2.010(8) A, respectively) in both molecules. Cis-
triplet of triplet pattern for the hydroxyl protons. Its 13
C
˚
spectrum revealed an axial CO at l +208.8 (2JPC=21.8
Hz) and equatorial COs at l +204.9 (2JPC=8.7 Hz).
An X-ray structural determination of a single-crystal,
grown from hexane, confirmed the overall structure of
this pentacarbonyl phosphine complex and also revealed
the presence of both intra- and intermolecular hydro-
gen-bonding. Two independent molecules were located
bond angles around the metal deviate by no more than
2.7° from orthogonality. Selected bond distances and
angles are listed in Table 2.
A bifurcated hydrogen bond centered at O(7) links
the two independent molecules with O(7)···O(7%) at
˚
˚
2.752(7) A while the intramolecular O(6)···O(7) is also at
2.718(7) A and the O(6)···O(7)···O(7%) angle is 91.3° (Fig.
2).
Table 1
Crystallographic data
Table 2
˚
Selected bond distances (A) and angles (°)
Crystal parameters
Formula
C13H11MoO7P
406.13
˚
Bond distances (A)
Formula weight
Crystal system
Space group
Mo(1)–C(1)
Mo(1)–C(3)
Mo(1)–C(4)
Mo(1%)–C(1%)
Mo(1%)–C(5%)
Mo(1%)–C(4%)
2.014(8)
2.037(9)
2.045(9)
2.010(8)
2.037(9)
2.039(9)
Mo(1)–C(2)
Mo(1)–C(5)
Mo(1)–P(1)
Mo(1%)–C(2%)
Mo(1%)–C(3%)
Mo(1%)–P(1%)
2.010(9)
2.041(9)
2.483(2)
2.031(9)
2.029(10)
2.498(2)
triclinic
¯
P1
˚
a (A)
10.283(2)
12.240(2)
13.316(3)
96.03(3)
94.90(3)
91.55(3)
1.625
˚
b (A)
˚
c (A)
h (°)
i (°)
Bond angles (°)
k (°)
C(1)–Mo(1)–C(2)
C(2)–Mo(1)–C(3)
C(2)–Mo(1)–C(5)
C(1)–Mo(1)–C(4)
C(3)–Mo(1)–C(4)
C(1)–Mo(1)–P(1)
C(3)–Mo(1)–P(1)
C(4)–Mo(1)–P(1)
C(1%)–Mo(1%)–C(5%)
C(1%)–Mo(1%)–C(3%)
C(5%)–Mo(1%)–C(3%)
C(2%)–Mo(1%)–C(4%)
C(3%)–Mo(1%)–C(4%)
C(2%)–Mo(1%)–P(1%)
C(3%)–Mo(1%)–P(1%)
89.0(3)
88.6(3)
93.0(3)
90.0(3)
88.8(3)
179.0(2)
88.6(2)
90.4(2)
90.0(3)
91.5(3)
178.4(3)
176.1(3)
89.8(3)
92.7(2)
90.5(2)
C(1)–Mo(1)–C(3)
C(1)–Mo(1)–C(5)
C(3)–Mo(1)–C(5)
C(2)–Mo(1)–C(4)
C(5)–Mo(1)–C(4)
C(2)–Mo(1)–P(1)
C(5)–Mo(1)–P(1)
C(1%)–Mo(1%)–C(2%)
C(2%)–Mo(1%)–C(5%)
C(2%)–Mo(1%)–C(3%)
C(1%)–Mo(1%)–C4)
C(5%)–Mo(1%)–C(4%)
C(1%)–Mo(1%)–P(1%)
C(5%)–Mo(1%)–P(1%)
C(4%)–Mo(1%)–P(1%)
92.2(3)
90.9(3)
176.5(3)
177.2(3)
89.7(3)
90.7(2)
88.2(2)
88.0(3)
91.6(3)
88.2(3)
88.7(3)
90.5(3)
177.9(2)
88.0(2)
90.6(2)
Dcalc (g cm−3
)
Temperature (K)
v(Mo Ka) (cm−1
Data collection
Diffractometer
Monochromator
Radiation
293
9.14
)
Siemens P4
graphite
Mo Ka (u=0.71073 A)
4.0–50.0
5064
3983
˚
2q Scan (°)
Independent reflections
Independent observed reflections
Refinement
R(F) (%)
5.26
9.03
1.2
R(wF2) (%)
GOF

J.C. Kane et al. / Inorganica Chimica Acta 287 (1999) 209–211
211
mal parameters, and bond distances and angles have
been deposited with the Cambridge Crystallographic
Data Centre as CCDC No. 110872. Copies of this
information may be obtained free of charge from The
Director, CCDC, 12 Union Road, Cambridge, CB2
1EZ, UK (Fax: +44-1223-336-033; e-mail: deposit@
cam.ac.uk or www: http://www.ccdc.cam.ac.uk).
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Fig. 2. Intermolecular H-bonding linking the two molecules of
Mo(CO)5[PPh(CH2OH)2].
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4. Supplementary material
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Tables of X-ray experimental details and crystallo-
graphic data, full atomic coordinates, anisotropic ther-
.