1-METHYL-2-CHLORO-3-DICHLOROPHOSPHINYL-1,3,2-LAMBDA(3)-DIAZAPHOSPHORINANE AND 1-METHYL-2-METHOXY-3-DIMETHOXYPHOSPHINYL-1,3,2-LAMBDA(3)-DIAZAPHOSPHORINANE AS LIGANDS IN TRANSITION-METAL COMPLEXES - SYNTHESIS AND STRUCTURE OF TETRACARBONYLMOLYBDENUM(0) COORDINATION-COMPOUNDS AND AN IONIC BIS-CHELATE PLATINUM(II) CHLORIDE COMPLEX

The reaction of 1-methyl-2-chloro-3-dichlorophosphinyl-1,3,2 lambda(3)-diazaphosphorinane 1 with (norbornadiene)tetracarbonylmolybdenum(0) in a 2:1 molar ratio furnished cis-bis(1-methyl-2-chloro-3-dichlorophosphinyl-1,,3,2-diazaphosphorinane)tetracarbonylmolybdenum(0) 2. In 2, one ligand 1 is bonded to Mo(0) via the (P) under bar Cl group, the other through the (P) under bar Cl-2, group. 1-Methyl-2-methoxy-3-dimethoxyphosphinyl-1,3,2 lambda(3)-diazaphosphorinane 3 reacted with norbornadienetetracarbonyl-molybdenum(0) to form the chelate complex cis-(1-methyl-2-methoxy-3-dimethoxyphosphinyl-1,3,2-diazaphosphorinane)tetracarbonylmolybdenum(0) 4, in which one molecule of the ligand 3 is attached to Mo(0) in a chelating fashion, coordinating through both the (P) under bar OCH3 and the (P) under bar(OCH3)(2) group. In the reaction of 3 with (COD)PtCl2 (COD = 1,5-cyclooctadiene) in a 2:1 molar ratio the ionic bis-chelate complex cis-bis(1-methyl-2-methoxy-3-dimethoxyphosphinyl-1,3,2-diazaphosphorinane)-platinum(II)chloride 5 was formed. Two molecules of 3 are coordinated to Pt(II) in the same fashion as in 4. The characterization of 2, 4, 5 is based on their H-1-, C-13- and P-31-n.m.r.-spectra, and their mass spectra and infrared spectra. The structure of the chelate complex 4 was confirmed by a single-crystal X-ray structure analysis. The ligand 3 is coordinated via both phosphorus atoms; the four-membered ring has a very narrow ''bite'' angle of 64.08(3)degrees, and the molybdenum atom thus displays distorted octahedral coordination geometry. Both phosphorus atoms have strongly distorted tetrahedral coordination geometry. The six-membered heterocycle assumes a chair conformation.