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Based upon the experimentally known but yet unexplained very different reactivities of the two isoelectronic and isolobal intermediates Pt(PMe 3 ) 2  and Pt(PEt 3 ) 2 , the electronic structure and bonding capability of such 14 electron fragments as a function of their geometry (P-Pt-P angle α, determined by the phosphane cone angle) are investigated using molecular orbital calculations. A decrease of the P-Pt -P angle leads to an exceptionally pronounced energy ascent of the b 2 -HOMO of Pt(PR 3 ) 2  species, which, as a consequence, might lead to unusual reactivity patterns and bonding capabilities of 1,3-diphosphaplatinacyclobutane fragments, for which an extreme electronic situation is enforced by steric constraints. Dichloro[η 2 -bis(di-r-butylphosphino) methane]platinum(II), Pt(dtbpm)Cl 2 , is synthesized as a potential precursor of Pt(dtbpm), in order to allow experimental investigations of this taylor made four-membered ring chelate complex of Pt(0). The crystal and molecular structure of Pt(dtbpm)Cl 2  · 2 CHCl 3  has been determined by X-ray diffraction.

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Synthese und Molekülgeometrie von Dichloro[η 2 -bis(di-r-butylphosphino)methan]pIatin(II), Pt(dtbpm)Cl 2 . Die Elektronenstruktur von 1,3-Diphosphaplatinacyclobutan-Fragmenten / Synthesis and Molecular Structure of Dichloro[η 2 -bis(di-t-butylphosphino)methane]platinum(II), Pt(dtbpm)Cl 2 . The Electronic Structure of 1,3-Diphosphaplatinacyclobutane Fragments