Experimental and theoretical studies of carbodiphosphorane-CX2 adducts with unusual bonding situations: preparation, crystal structures, and bonding analyses of S2CC(PPh3)2, O2CC(PPh3)2, and [(CO)4MS2CC(PPh3)2] (M = Cr, Mo, W).
We report about the first X-ray structure analyses of the CS2 and CO2 adducts with carbodiphosphorane C(PPh3)2 and the synthesis and X-ray structure analysis of group 6 carbonyl complexes with compound S2CC(PPh3)2 as a ligand [(CO)4MS2CC(PPh3)2] (M = Cr, Mo, W). The nature of the carbon-carbon bonding in X2CC(PPh3)2 and in the model compounds X2CC(PH3)2 and the metal-ligand bonding in [(CO)4MoS2CC(PH3)2] have been analyzed with charge and energy decomposition methods using DFT calculations. Carbodiphosphoranes C(PR3)2 are double electron pair donors having sigma- and pi-carbon lone-pair orbitals as the two highest occupied MOs.
Petz
Wolfgang
W
Fachbereich Chemie, Philipps-Universität Marburg, Hans-Meerwein-Strasse, D-35032 Marburg, Germany. petz@staff.uni-marburg.de
Kutschera
Christian
C
Heitbaum
Maya
M
Frenking
Gernot
G
Tonner
Ralf
R
Neumüller
Bernhard
B