134681-63-3Relevant academic research and scientific papers
(Phosphinoalkyl)silyl complexes. 10. Formation of chelated bis[(diphenylphosphinoethyl)diorganosilyl]platinum(II) complexes. Precoordination through phosphorus, intermediacy of a platinum(IV) disilyl, and diastereoisomerism at planar platinum(II) in chelate-assisted hydrosilylation
Grundy, Stephen L.,Holmes-Smith, Rupert D.,Stobart, Stephen R.,Williams, Mark A.
, p. 3333 - 3337 (2008/10/08)
Addition of the silane PPh2CH2CH2SiMe2H (chelH, 1a) to Pt(COD)2 (COD = cycloocta-1,5-diene) affords in high yield the cis-bis chelate Pt(chel)2 (2); formation of the same product from Pt(COD)(X)Y (X = Y = Me; X = Me, Y = Cl) has been shown by NMR spectroscopy (1H, 31P, 195Pt) to proceed via prior coordination of chelH through P to afford Pt(chelH)2(X)(Y) (cis and trans isomers) and through intermediacy of PtH(chel)2Cl (22) in which P trans to Si at Pt(IV) leads to an exceptionally low 2J(Pt-P) = 1084 Hz. Cleavage of Pt-Si bonds in 2 by HCl can be controlled to give the monochelate species Pt(chel)(chelH)Cl (7), from which chelH is displaced by PMe2Ph, or trans-PtH(PPh2CH2CH2SiMe2Cl) 2Cl (9). Products related to 9 result from Pt-Si bond cleavage by I2 or MeI. Using the analogue PPh2CH2CH2SiMe(Ph)H (1c) of 1a, the analogue Pt-[PPh2CH2CH2SiMe(Ph)]2 (4) of 2 is obtained as a mixture of meso and racemic diastereomers in which the latter predominates, as is established by its separation and then reaction with optically pure (+)-2-methylbutyl iodide to give two diastereomeric products of Pt-Si bond cleavage as well as by single-crystal X-ray diffraction.
