Gold–ruthenium compounds containing bridging phosphide or thiolate groups: Crystal structures of the intermediate species [Ru3(CO)8L(μ3-η2,η4,η3-{Me3SiCC(C2Fc)SC(Fc)CSCCSiMe3})] (L=NMe3 or PPh2H)

A Novel Bis(phosphido)pyridine [PNP]2− Pincer Ligand and Its Potassium and Bis(dimethylamido)zirconium(IV) Complexes

“…As a consequence, many bridging phosphido complexes have been isolated, a result of long M-P bonds and reduced steric congestion, as compared with amido complexes. [20][21][22] Another feature that distinguishes phosphine (and X type phosphido) from amine (and X type amido) ligands is the high energy barrier for inversion at phosphorus, thus affording chirogenicity to asymmetrically substituted phosphines at ambient temperatures (the inversion barrier of NMe 3 has been estimated at 8 kcal/ mol vs 45 kcal/mol for PMe 3 ). 23 Glueck and co-workers have reported extensively on the synthesis and structural elucidation of late-metal complexes stabilized by monodentate terminal and bridging phosphides.…”

“…Secondary phosphines (PHR 2 ) and their conjugate phosphides (PR 2 − ) have been much less studied as ligands, no doubt a result of their toxicity and susceptibility to autoxidation in air. , Using standard organic techniques to synthesize and/or purify secondary phosphines requires the extensive use of borane, oxide, sulfide, and selenide protecting groups. − Phosphides, generally obtained by deprotonation of a secondary phosphine or reduction of a chlorophosphine, are particularly interesting ligands, given their ability to coordinate in either an X type or LX type fashion, a feature common to anionic ligands with one available π-electron pair. − Unlike amide ligands, phosphides are soft donors whose lone pair resides in a more extensive orbital that can coordinate in an L type fashion to another metal in polynuclear complexes. As a consequence, many bridging phosphido complexes have been isolated, a result of long M−P bonds and reduced steric congestion, as compared with amido complexes. − Another feature that distinguishes phosphine (and X type phosphido) from amine (and X type amido) ligands is the high energy barrier for inversion at phosphorus, thus affording chirogenicity to asymmetrically substituted phosphines at ambient temperatures (the inversion barrier of NMe 3 has been estimated at 8 kcal/mol vs 45 kcal/mol for PMe 3 ) …”

Synthesis of homo- and heteronuclear ruthenium–gold clusters with diphosphine and thiolato bridged ligands. Single crystal molecular structure of [Ru3(CO)10(μ-AuPPh3)(μ-SC5H4N)] and [Ru3(CO)8(μ-H)(μ-SC5H4N)(μ-dppe)]

“…For example, the formation of a thiolato group bridging a ruthenium and a gold atom, which are not bonded, has been described [18] and the reactions between ruthenium clusters with bidentate diphosphine gold ligands like [Au 2 (m-dppm)Cl 2 ] have produced mixed metal compounds where the diphosphine ligand remained attached to the gold atoms [19,20]. However, there are no reports of rutheniumegold cluster with both thiolato and bidentate phosphine ligands coordinated to the metallic skeletal fragment.…”