Phosphinsubstituierte Chelatliganden, II [1] Thiocarbamoylphosphinsulfid-und -oxid-Komplexe des Mangans und Rheniums / Phosphine Substituted Chelate Ligands, II [1] Thiocarbamoylphosphine Sulfide and Oxide Complexes of Manganese and Rhenium

Abstract

<jats:title>Abstract</jats:title><jats:p> Thiocarbamoylphosphine sulfides 1 a-c and oxides 2 a-c are ambidentate chelating ligands which may form monomeric or dimeric complexes with carbonylmetal halides. The reaction of 1 a-c with ClMn(CO)<jats:sub>5</jats:sub> and ClRe(CO)<jats:sub>5</jats:sub> yields the monomeric cw-tetracarbonyl complexes 3 a-c and 4 a-c with S,S'-coordination. The phosphine oxides 2 a-c first form tetracarbonyl complexes which dimerize spontaneously under loss of CO to give the anfi-fac-tricarbonyl complexes 6 a-c and 6 a with bridging three-coordinate sulfur. On refluxing in n-hexane solution, 8 a-c and 4b, c are converted into the corresponding dimers 7 a-c and 8 b, c. Dissolving of 7 b, c in CH<jats:sub>2</jats:sub>Cl<jats:sub>2</jats:sub> leads to re-formation of 8 b, c, the free ligands 1 b, c and inorganic manganese compounds.</jats:p>

trans-Bis[dicyclohexylphosphino-N-phenyl(thioformamido)]platinum(II): Pt[(c-C6H11)2PC(S)=N(C6H5)]2

“…The title compound was synthesized by adding excess N(C2Hs) 3 to a stirred dichloromethane solution of CI2Pt[(C6Hs)CN]2 (Hartley, 1973) and (c-C6Hll)2PC(S)N(H)(C6Hs) (Kunze & Antoniadis, 1981) procedure on 25 reflections (11 < 0 < 19°). Analytical absorption correction applied (Sheldrick, 1976) (Sheldrick, 1976) and those for neutral Pt corrected for f' andf" (Hamilton & Ibers, 1974).…”

Phosphinsubstituierte Chelatliganden, XX [1] Darstellung und diastereoselektive Komplexierung von chiralen Phosphinothioformamiden, Ph2P(X)C(S)NHCHMePh (X = 2 e- , O, S) / Phosphine-Substituted Chelate Ligands, XX [1] Synthesis and Diastereoselective Complexation of Chiral Phosphinothioformamides, Ph2P(X)C(S)NHCHMePh (X = 2e-, O, S)

“…Die r(C =N )-V alenzschwingung der Thioformimidato-Komplexe 2a, c und 3a, c absorbiert bei 1570 bzw. 1540 cm-1 [9,15], während im Spektrum der S,N-koordinierten Thioformamido-Komplexe 2b, 3b keine charakteristische Thioamid-Bande zu beobachten ist [24], Die Diastereom eren A und B der P,S-und S,SChelatkomplexe unterscheiden sich im 'H-NM RSpektrum in den chemischen Verschiebungen der CsH5-und CH 3-Signale. Das M ultiplett des MethinProtons wird meist vom Ringsignal überdeckt und ist als Sonde weniger geeignet.…”