SYNTHESIS AND CHARACTERIZATION OF NOVEL DINUCLEAR AND CATIONIC CYCLOBUTADIENE PLATINUM COMPLEXES

Citation
M. Gerisch et al., SYNTHESIS AND CHARACTERIZATION OF NOVEL DINUCLEAR AND CATIONIC CYCLOBUTADIENE PLATINUM COMPLEXES, Journal of organometallic chemistry, 570(1), 1998, pp. 129-139
Citations number
19
Categorie Soggetti
Chemistry Inorganic & Nuclear","Chemistry Inorganic & Nuclear
ISSN journal
0022328X
Volume
570
Issue
1
Year of publication
1998
Pages
129 - 139
Database
ISI
SICI code
0022-328X(1998)570:1<129:SACOND>2.0.ZU;2-J
Abstract
Reactions of the cyclobutadiene platinum complexes [PtCl2(C4R4)](R = M e 1a, R = Et 1b) with diphosphines (Ph2PPPh2)-P-boolean AND ((boolean AND) = -c-=c- (dppa), -CH2- (dppm), -(CH2)(2)- (dppe), -(CH2)(3)- (dpp p), -(CH2)(4)- (dppb)) in a 2:1 molar ratio result in formation of nov el binuclear cyclobutadiene platinum complexes [{PtCl2(C4R4)}(mu-(Ph2P PPh2)-P-boolean AND)] (R = Me 2, Et 3). In contrast, reactions in equi molar ratio lead to formation of cationic complexes with dppe, dppp an d dppb [PtCl(C4R4){Ph2P(CH2)(n)PPh2}]Cl (n = 2-4, R = Me 5, Et 6). Com plexes 2, 3 and 5, 6 were fully characterized by microanalysis and by NMR and IR spectroscopies. Structural characterization of [{PtCl2(C4Me 4)}(2)(mu-Ph2PCH2PPh2)] (2b) reveals a piano-stool coordination at eac h platinum center defined by the mu(4)-C4Me4 ligand, two Cl atoms and one P atom. The P-C-P angle of 131.0(4)degrees is larger than that exp ected for tetrahedral geometry. The X-ray structure of [PtCl(C4Me4){Ph 2P(CH2)(3)PPh2}]Cl . CH2Cl2 (5b . CH2Cl2) reveals a Pt atom coordinate d by the eta(4)-C4Me4 ligand, chloride and the two phosphorus donors i n a piano-stool conformation. In the solid state, these cations are ar ranged to form channels with a diameter of 13.8 Angstrom in which solv ent molecules (CH2Cl2) are embedded. (C) 1998 Elsevier Science S.A. Al l rights reserved.