Synthesis and reactivity of mononuclear molybdenum phosphido complexes, [Mo(CO)2{P(Cl)R}(η-C5H5)][R = CH(SiMe3)2 or NCMe2CH2CH2CH2CMe2]. X-Ray crystal structures of [Mo(CO)2{P(X)(NCMe2CH2CH2CH2CMe2)}(η-C5H5)](X = Cl or NMe2) and [Mo2(CO)4{µ-P2[CH(SiMe3)2]2}(η-C5H5)2]
- 1 January 1988
- journal article
- research article
- Published by Royal Society of Chemistry (RSC) in J. Chem. Soc., Dalton Trans.
- No. 8,p. 2127-2134
- https://doi.org/10.1039/dt9880002127
Abstract
Reaction of K[Mo(CO)3(η-C5H5)] with PCl2R affords the mono-chlorophosphido species, [Mo(CO)2{P(Cl)R}(η-C5H5)][R = 2,2,6,6-tetramethyl-1-piperidyl (tmp), (1), or CH(SiMe3)2, (3)]. Both (1) and (3) contain a three-electron donor phosphido ligand featuring Mo–P multiple bonding and a trigonal-planar configuration at phosphorus. Compound (1) has been characterised by X-ray diffraction. The reaction of (1) with Li[NMe2] affords [Mo(CO)2{P(NMe2)(tmp)}(η-C5H5)](7), which has also been characterised by X-ray crystallography. The synthesis of (7) demonstrates the reactivity of the P–Cl functionality but (7) may also be prepared by direct reaction between K[Mo(CO)3(η-C5H5)] and PCl(NMe2)(tmp). Reduction of (3) with sodium dihydronaphthylide leads to a coupling reaction via P–P bond formation resulting in the cis-diphosphene complex [Mo2(CO)4{µ-P2[CH(SiMe3)2]2}(η-C5H5)2](8), which was characterised by X-ray diffraction. Spectroscopic evidence is also presented for a dimolybdenum diphosphinidene complex, isomeric with (8).Keywords
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