Bis(trimethylsilyl)phosphido complexes. Part 3. Syntheses, structures and reactions of [bis(trimethylsilyl)phosphido]-zirconocene(IV) complexes and the X-ray structure of {AlMe2[µ-P(SiMe3)2]}2
- 1 January 1991
- journal article
- research article
- Published by Royal Society of Chemistry (RSC) in J. Chem. Soc., Dalton Trans.
- No. S,p. 939-948
- https://doi.org/10.1039/dt9910000939
Abstract
The complexes [Zr(cp)2(PR2)X](cp =η-C5H5; R = SiMe3; X = Cl, 2; PR2, 3; or Me, 6) and [Zr(η-C5H4R)2(PR2)Y](Y = Cl, 4; or PR2, 5) were obtained from [{Li(µ-PR2)(thf)2}2]1(thf = tetrahydrofuran) and [Zr(cp)2Cl2] or [Zr(η-C5H4R)2Cl2], respectively. Each of 2, 3, and 6 was treated with a variety of reagents causing scission of the Zr–P bond. Two types of reactions were observed: (i) substitution or (ii) insertion. Examples of (i) are the reaction of (a) complex 3 with Mel to afford [Zr(cp)2I(PR2)]7, (b)2 with LiOR′(R′= C6H2But 2-2,6-Me-4), SiMe3(N3), Mel or EtOH yielding [Zr(cp)2Cl(Z)](Z = OR′, 8; N3, 9; or I, 10) or [{Zr(cp)2Cl}2(µ-O)]11, respectively and (c)2 with (AlMe3)2 to furnish [AlMe2(µ-PR2)]212. The X-ray structure of 12 shows a planar nearly square Al2P2 ring [Al–P 2.460(2) and 2.453(2)Å, P–Al–P′89.4(1), Al–P–Al′ 90.60(5)°], a configuration which is retained in hydrocarbon solution (1H and 29Si NMR spectroscopy). Type (ii) reactions were those between (a)2 and a diazoalkane N2CR′R″ yielding [[graphic omitted](PR2)}](R′= R″= Ph, 13; or R′= H, R″= CO2Et, 14), (b)2 or 6 with CS2, affording [Zr(cp)2{S2C(PR2)}X](X = Cl, 15; or Me, 16), and (c)3 with white phosphorus to give [[graphic omitted]]17. Each of the complexes 3 and 6 reacted with sulphur to furnish [{Zr(cp)2(µ-S)}2], which was also obtained by thermolysis of 15. The thermolysis of 2, 4 or 6 led to elimination of SiMe3X (X = Cl or Me).Keywords
This publication has 93 references indexed in Scilit:
- Synthesis and characterization of phosphinosilylalanes from [(CH3)3Si]3Al. Crystal and molecular structure determinations of {[(CH3)3Si]2AlP(C6H5)2}2, {[(CH3)3Si]2AlP(C6H5)[Si(CH3)3]}2, {[(CH3)3Si]2AlP(H)(c-C6H11)}3, and [{[(CH3)3Si]2N}(C6H5)P]2Organometallics, 1989
- PxUnits as Complex LigandsComments on Inorganic Chemistry, 1987
- Phosphine complexes of main group elements: Al[C(PMe2)2X]3(X = PMe2 or SiMe3), the first examples of six-co-ordinate aluminium phosphine complexesJournal of the Chemical Society, Chemical Communications, 1985
- Transition-metal complexes of organoaluminum phosphides. Synthesis, characterization, and crystal and molecular structure of Cr(CO)5(PPh2Al)(CH2SiMe3)2.NMe3Inorganic Chemistry, 1983
- Synthesis and structure of bis(2,4,6-tri-tert-butylphenyl)diphosphene: isolation of a true phosphobenzeneJournal of the American Chemical Society, 1981
- The Transition Metal‐Nitrogen Multiple BondAngewandte Chemie International Edition in English, 1981
- Alkyl-bridged complexes of the d- and f-block elements. Part 1. Di-µ-alkyl-bis(η-cyclopentadienyl)metal(III)dialkylaluminium(III) complexes and the crystal and molecular structure of the ytterbium methyl speciesJ. Chem. Soc., Dalton Trans., 1979
- Schwingungsspektren und kraftkonstanten von silyl- und trimethylsilyl-verbindungen von elementen der 5. gruppeSpectrochimica Acta Part A: Molecular Spectroscopy, 1970
- Preparation and properties of aluminum phosphideJournal of Inorganic and Nuclear Chemistry, 1963
- PROTON MAGNETIC RESONANCE SPECTRUM OF ALUMINUM TRIMETHYL DIMERJournal of the American Chemical Society, 1960