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Syntheses, spectroscopic characterization and electronic structure of cyclopropenylidene ligated platinum complexes
Author(s) -
Miki Sadao,
Ogno Toshinobu,
Iwasaki Hideaki,
Yoshida ZenIchi
Publication year - 1988
Publication title -
journal of physical organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.325
H-Index - 66
eISSN - 1099-1395
pISSN - 0894-3230
DOI - 10.1002/poc.610010604
Subject(s) - chemistry , platinum , stereochemistry , chemical shift , carbon 13 nmr , double bond , linkage isomerism , trans effect , coupling constant , crystallography , crystal structure , polymer chemistry , organic chemistry , catalysis , physics , particle physics , metal
New series of platinum complexes of cyclopropenylidenes of the types of PtX 2 (CP) 2 and trans ‐PtX(PBu 3 ) 2 (CP) have been synthesized, where CP is di‐ t ‐butylcyclopropenylidene (BCP) or bis(diisopropylamino)cyclopropenylidene (ACP). The 13 C‐NMR chemical shifts, and 13 C− 195 Pt coupling constants ( 1 J PtC ) for the complexes are discussed in comparison with those values derived from closely related series of compounds, trans ‐PtCl(PR 3 ) 2 L; L CH 3 , C 6 H 5 and CCBu‐ t . An excellent linear relationship through the origin was obtained between 1 J PtC and the formal ‘ s ’ % character of the carbon directly bonded to Pt for the series trans ‐PtCl(PR 3 ) 2 L in which the PtC bond is regarded as a pure σ‐linkage, whereas 1 J PtC deviates largely from this relationship when pπdπ bonding interaction possibly exists in the PtC bond. The NMR data suggest the strong nmr trans ‐influence of the cyclopropenylidenes and that in the PtCP bond the σ‐interaction is appreciable but the π‐interaction is negligible.