[BH₃·PPh₂CH₂C₆H₄CH₂PPh₂·Ru(p-cym)Cl₂]:  A New Bifunctional Compound and Prototype of a Linked Borane/Metal Cluster Species

Abstract

The species [BH3·PPh2CH2C6H4CH2Ph2P·(p-cym)RuCl2], which is a bidentate phosphine ligand with a complexed Ru moiety at one end and a borane(1) group at the other end, has been prepared and characterized spectroscopically and the crystal structure reported. The molecule adopts a conformation in which the P atoms are syn to each other and the species exhibits novel long range 31P−31P NMR coupling.

Synthesis and transition metal chemistry of a bridging diphosphinite, 1,4 bis(diphenylphosphinoxy)benzene

“…One of the phenyl rings on phosphorus is almost perpendicular to the plane of hydroquinone moiety. The phosphorus atoms are in a distorted tetrahedral geometry with maximum deviation shown by the O1eP1eC1 bond where the bond angle is 97.20 (12) .…”

Reactions of Boranes and Metallaboranes with Phosphines

“…Reactions with the bidentate bases dppm, dppe, and dppp afford similar products to IV, e.g., {[(PPh 3 ) 2 (CO)OsB 4 H 7 ][BH 2 ؒ(dppe)]} (V) [6]. However, in the case of dppe and dppp, the species of the type V undergo intramolecular substitution to afford a second species [(PPh 3 )(CO)OsB 4 H 7 -η 2 -3,2-{BH 2 ؒ(dppe)] (VI).…”

“…We discovered that for other metals it was easier to push the equilibrium shown in Scheme 6, to afford bidentate dppm species of type XXI using [PF 6 ] -salts. We also derivatized the same series of phosphines with BH 3 at one end and a metal moiety at the other end to form such species as BH 3 ؒPPh 2 (linker)PPh 2 ؒML n [16]. One goal of this series of experiments was to compare these species with those involving more complex borane moieties such as those described above.…”

“…This paper will cover several aspects of recent work, all of which involves the formation of phosphorus to boron bonds or reactions of phosphine boranes. At IMEBORON X [5], we described work which was stimulated by some results we obtained from studies of the reactions of the metallahexaborane [2,2,2-(PPh 3 ) 2 (CO)-nido-2-OsB 5 H 9 ] (I) with phosphines and the extensions of that work to reaction with bidentate phosphines [6]. We also described further extensions of the work to reactions of bidentate bases with the unsaturated cluster [8,8- (PPh 3 ) 2 -nido-8,7-RhSB 9 H 10 ] (II) [7].…”

Reactions of Boranes and Metallaboranes with Phosphines

“…The reaction of phosphines with (I) gives species of the type [2,2,2-(PPh 3 ) 2 (CO)-nido-2-OsB 4 H 7 -3-BH 2 ؒPR 3 ] (IV) which contain a pendent BH 2 ؒPR 3 group. Reactions with the bidentate bases dppm, dppe, and dppp afford similar products to IV, e.g., {[(PPh 3 ) 2 (CO)OsB 4 H 7 ][BH 2 ؒ(dppe)]} (V) [6]. However, in the case of dppe and dppp, the species of the type V undergo intramolecular substitution to afford a second species [(PPh 3 )(CO)OsB 4 H 7 -η 2 -3,2-{BH 2 ؒ(dppe)] (VI).…”