Organo-complexes of platinum derived from methyl vinyl ketone and bis(cyclo-octa-1,5-diene)platinum; X-ray crystal structure of (1,3-diacetylbutane-1,4-diyl)bis(triphenylphosphine)platinum

Abstract

Organo-complexes of Platinum derived from Methyl Vinyl Ketone and Bis(cyc10-octa-I ,5-diene)platinum ; X-Ray Crystal Structure of (1,3-Diacetyl butane-I ,$-diyl) bis(triphenylphosphine)platinum

Synthesis and X-ray Crystal Structure of a Novel Zinc “Ate Complex”, [Li(TMEDA)]2Zn(CH2SiMe2SiMe2CH2)2

“…The "ate complexes" are normally prepared by reaction of dilithium butanes with suitable d-block metal complexes. Attempts to prepare a corresponding platinum compound by use of LiCH 2 SiMe 2 -SiMe 2 CH 2 Li (1) failed, because the reaction of 1 and (COD)PtCl 2 (2) in the presence of (CH 3 ) 2 NCH 2 -CH 2 N(CH 3 ) 2 (TMEDA) gives the neutral complex (COD)Pt(CH 2 SiMe 2 SiMe 2 CH 2 ) (3), whereas under the same conditions LiCH 2 CMe 2 CMe 2 CH 2 Li (4) reacts with 2 in the presence of TMEDA to afford the "ate complex" [Li(TMEDA)] 2 Pt(CH 2 CMe 2 CMe 2 CH 2 ) 2 (5). 10 This result indicates that 1 is a less reactive agent than 4 and that it would be more difficult to produce "ate complexes" from 4 and d-block metal complexes.…”

“…Metallacycles are of great significance as intermediates of numerous catalytic reactions, such as the [2 + 2] cycloaddition of olefins, the oligomerization of 1,2- and 1,3-dienes, the isomerization of strained cyclic hydrocarbons, olefin metathesis, and ring-opening metathesis polymerization (ROMP). , Especially mechanistic and structural investigations on metallacyclopentane complexes of the type L m M(CH 2 CH 2 CH 2 CH 2 ) (M = d-metal; L = neutral ligand) have considerably contributed to a better understanding of the catalytic behavior of such systems, and they also have shown the influence of the neutral ligand L on their structure, thermal stability, and reactivity. , Thus it was of interest to prepare metallacyclopentane compounds, in which exclusively butane-1,4-diyl ligands are bonded to the central atom.…”