(Phospinoalkyl)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

Journal Article · Wed Aug 21 00:00:00 EDT 1991 · Inorganic Chemistry; (United States)

DOI:https://doi.org/10.1021/ic00017a021· OSTI ID:6837289

Grundy, S L; Holmes-Smith, R D; Stobart, S R; Williams, M A ^[1]

---

1. Univ. of Victoria, British Columbia (Canada)

Addition of the silane PPh[sub 2]CH[sub 2]CH[sub 2]SiMe[sub 2]H (chelH, 1a) to Pt(COD)[sub 2] (COD = cycloocta-1,5-diene) affords in high yield the cis-bis chelate Pt(chel)[sub 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 ([sup 1]H, [sup 31]P, [sup 195]Pt) to proceed via prior coordination of chelH through P to afford Pt(chelH)[sub 2](X)(Y) (cis and trans isomers) and through intermediacy of PtH(chel)[sub 2]Cl (22) in which P trans to Si at Pt(IV) leads to an exceptionally low [sup 2]J(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 PMe[sub 2]Ph, or trans-PtH(PPh[sub 2]CH[sub 2]SiMe[sub 2]Cl)[sub 2]Cl (9). Products related to 9 result from Pt-Si bond cleavage by I[sub 2] or MeI. Using the analogue PPh[sub 2]CH[sub 2]CH[sub 2]SiMe(Ph)H (1c) of 1a, the analogue Pt-[PPh[sub 2]CH[sub 2]CH[sub 2]SiMe(Ph)][sub 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.

• OSTI ID: 6837289
• Journal Information: Inorganic Chemistry; (United States), Journal Name: Inorganic Chemistry; (United States) Vol. 30:17; ISSN 0020-1669; ISSN INOCAJ
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
CHEMICAL PREPARATION
CHEMICAL REACTIONS
COHERENT SCATTERING
COMPLEXES
COUPLING CONSTANTS
DATA
DAYS LIVING RADIOISOTOPES
DIFFRACTION
EVEN-ODD NUCLEI
EXPERIMENTAL DATA
HEAVY NUCLEI
HYDRIDES
HYDROGEN COMPOUNDS
INFORMATION
INTERNAL CONVERSION RADIOISOTOPES
ISOMERIC TRANSITION ISOTOPES
ISOTOPES
LIGHT NUCLEI
MAGNETIC RESONANCE
NUCLEAR MAGNETIC RESONANCE
NUCLEI
NUMERICAL DATA
ODD-EVEN NUCLEI
ORGANIC COMPOUNDS
ORGANIC SILICON COMPOUNDS
PHOSPHORUS 31
PHOSPHORUS ISOTOPES
PLATINUM 195
PLATINUM COMPLEXES
PLATINUM ISOTOPES
RADIOISOTOPES
RESONANCE
SCATTERING
SILANES
SILICON COMPOUNDS
STABLE ISOTOPES
STEREOCHEMISTRY
SYNTHESIS
TRANSITION ELEMENT COMPLEXES
X-RAY DIFFRACTION