Organodiphosphines in Pt{η2-P(X)nP}(Cl)2 (n = 4, 5, 6, 7, 8, 10, 11, 15, 18) derivates: Structural aspects

This structural study includes over 70 Pt{η2-P(X)nP}(Cl)2 (n = 4, 5, 6, 7, 8, 10, 11, 15, 18) derivates in which organodiphosphines create wide varieties of the metallocyclic rings: 7 membered (PC4P (most common), POC2OP, PNC2NP, PSC2SP, PNC2OP; 8 membered (PC5P, PC2OC2P, PC2NC2P); 9 membered (PC6P, POC4OP); 10 membered (POC5OP, PC2OCOC2P; PC3OC3P); 11 membered (PC8P,PNC6NP,POC6OP), 13 membered (PC3NC2NC3P); 14 membered (P(C2Cl3C2P); 18 membered (PC4NC2NC2NC4P); and 21 membered (POC2NC10NC2OP). These complexes crystallized in three crystal classes: triclinic (15 examples) < orthorhombic (17 examples) < monoclinic (39 examples). In these complexes, the most common is a predominantly cis arrangement (68 examples) and only 3 examples with trans configuration. The total mean values of Pt–L bond distances in the complexes (cis vs trans configuration) are 2.232 Å (L = P), 2.353 Å (L = Cl) vs 2.312 and 2.307 Å, respectively. The structural data are compared and discussed with those found in cis-Pt(η2-P(X)nP)(Cl)2 (n = 1, 2, 3) in which organodiphosphines form four-PCP, PNP; five-PC-CP; PC═CP; six-PC3P, PNCNP, PCCOP, PCCNP, PCSCP, PCSiCP; membered metallocyclic rings. Some complexes are examples of distortion and cis–trans isomerism.