It is shown that ligand 1, designed to span trans‐positions, under appropriate conditions also gives cis‐mononuclear complexes of platinum (II). The structure of cis‐[PtCl2 (1)] (2) has been determined by single‐crystal X‐ray diffraction. The major distortion from square planar coordination is the P‐Pt‐P angle of 104.8°. Values of valence angles within the bidentate ligand indicate that this part of the molecule is very strained. Two phenyl groups, one on each phosphorus, lie almost parallel to each other separated by ca. 3.2–3.3 Å. The 1H‐NMR. data for this compound show that the π‐phenyl interactions observed in the solid state occur also in solution. The preparation and NMR.‐spectroscopic properties of trans‐ and cis‐[PtH(PPh3) (1)] [BF4] are reported.
Eine gewinkelte PtHPt‐Gruppierung ist das besondere Strukturmerkmal des Kations (1), das überraschenderweise aus trans‐[PtH(NO3)(Et3P)2] und Na[BPh4] entsteht. Im Gegensatz zu anderen zweikernigen Platinhydriden enthält (1) keine (stabilisierenden) zweizähnigen Donorliganden.
ChemInform Abstract trans-Complexes of the type PtMeX(P1-P1) such as (I) and (III) as well as PtHX(P1-P1) such as (IV) and (VI) are prepared. Their decompositions to the corresponding trans-hydride complexes (II) and (V), respectively, are studied. Some binuclear complexes are also obtained. Thus, the hydride-bridged one (IX) can be synthesized by reaction of the methanol analogue (VIII) with sodium format (VII) as shown. The hydridomethyl-bis(phosphine) complex (XII) is prepared via the γ-picoline analogue. The structure of the analogous diphosphine complex (XIII), substitution product from the bis(triphenylphosphine) analogue, is determined by X-ray analysis (space group P21/c, Z=4).
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