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Synthesis, spectroscopic and structural characterisation of chromium(0), molybdenum(0) and tungsten(0) complexes involving primary and secondary phosphines

Campbell, Tom, Gibson, Alexander M., Hart, Richard, Orchard, Simon D., Pope, Simon J. A. and Reid, Gillian 1999. Synthesis, spectroscopic and structural characterisation of chromium(0), molybdenum(0) and tungsten(0) complexes involving primary and secondary phosphines. Journal of Organometallic Chemistry 592 (2) , pp. 296-305. 10.1016/S0022-328X(99)00570-7

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Abstract

[M(CO)6] (M=Mo or W) reacts with 4.5 molar equivalents of L (L=PPh2H or PPhH2) in excess ethanolic NaBH4 to yield the fac-trisubstituted species [M(CO)3(L)3] in good yield, with no evidence for species with lower degrees of substitution. IR, 1H-, 13C{1H}-, 31P{1H}- and 95Mo-NMR spectroscopy on these compounds, together with X-ray crystallographic studies on two examples, confirm the fac-tricarbonyl arrangement both in solution and in the solid state. Similar reactions involving PCy2H yield only the cis-disubstituted species [M(CO)4(PCy2H)2]. Reaction of [M′(CO)4(nbd)] (M′=Cr or Mo) or [W(CO)4(TMPA) (TMPA=tetramethylpropylenediamine) with two molar equivalents of L (L=PPh2H, PPhH2 or PCy2H) or with one molar equivalent of L–L (L–L=o-C6H4(PH2)2, PhHPCH2CH2PHPh or PhHPCH2CH2CH2PHPh) in warm toluene solution give [M′(CO)4(L)2], [W(CO)4(L)2], [M′(CO)4(L–L)] or [W(CO)4(L–L)], respectively. Spectroscopic studies indicate that these all exist as cis-disubstituted species in solution and single-crystal X-ray analyses on three examples confirm this assignment in the solid state. The primary and secondary phosphines act as neutral two-electron donors in all cases with retention of the P–H functions. Trends in the spectroscopic and structural data are discussed.

Item Type: Article
Date Type: Publication
Status: Published
Schools: Chemistry
Subjects: Q Science > QD Chemistry
Uncontrolled Keywords: Chromium; Molybdenum; Tungsten; Primary phosphines; Secondary phosphines
Publisher: Elsevier
ISSN: 0022-328X
Last Modified: 04 Jun 2017 04:37
URI: http://orca.cf.ac.uk/id/eprint/41651

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