Derivative Chemistry of [Ru2(μ-bdt)(CO)6], a Binuclear Ruthenium(I) Carbonyl Complex Containing a Bridging Benzene-1,2-dithiolate Ligand

✍ Scribed by Javier A. Cabeza; M. Angeles Martínez-García; Víctor Riera; Diego Ardura; Santiago García-Granda; Juan F. Van der Maelen

• Book ID: 101280738
• Publisher: John Wiley and Sons
• Year: 1999
• Tongue: English
• Weight: 308 KB
• Volume: 1999
• Category: Article
• ISSN: 1434-1948
• DOI: 10.1002/(sici)1099-0682(199907)1999:7<1133::aid-ejic1133>3.0.co;2-v

✦ Synopsis

The known dithiolate-bridged ruthenium(I) complex [Ru 2 (µ-bdt)(CO) 4 }(µ-dppm)] n , which consists of binuclear {Ru 2 (µbdt)(CO) 4 } units linked to each other by bridging dppm bdt)(CO) 6 ] (1) (bdt = benzene-1,2-dithiolate) has been prepared in fair yield (55%) by the sequential treatment of ligands. The use of two equivalents of dppm leads to [Ru 2 (µbdt)(CO) 4 (η 1 -dppm) 2 ] in quantitative yield. The X-ray RuCl 3 •nH 2 O with carbon monoxide, benzene-1,2-dithiol and zinc in a one-pot reaction. Complex 1 reacts readily with diffraction structure of [Ru 2 (µ-bdt)(CO) 4 (PiPr 3 ) 2 ] (3c) confirms that the phosphane ligands are located in axial positions, cis monodentate phosphanes to give, stepwise, the penta-and tetracarbonyl derivatives [Ru 2 (µ-bdt)(CO) 6-n (PR 3 ) n ] (n = 1, 2;

to both sulfur atoms, and that the Ru-Ru distance is short [2.6753(7) A ˚]. A comparative study of the reactivity of R = Ph, Cy, iPr). However, the reaction of 1 with one equivalent of bis(diphenylphosphanyl)methane (dppm) complexes 1 and 3c with the electrophiles H + , [Au(PPh 3 )] + , and HgCl 2 has allowed the isolation of the derivatives [Ru 2 (µ-affords a mixture of complex 1 and the disubstituted derivative [Ru 2 (µ-bdt)(CO) 4 (η 1 -dppm) 2 ], in which the dppm H)(µ-bdt)(CO) 6-n (PiPr 3 ) n ][BF 4 ] (n = 0, 2), [Ru 2 Au(µ-bdt)(CO) 6-n -(PiPr 3 ) n (PPh 3 )][BF 4 ] (n = 0, 2) and [Ru 2 HgCl 2 (µ-bdt)(CO) 6-n -ligands are monodentate. This mixture is subsequently transformed into a polymeric material of formula [{Ru 2 (µ-(PiPr 3 ) n ] (n = 0, 2), respectively.

complexes, probably as a consequence of the lack of a con- [a] Departamento de Quı ´mica Orga ´nica e Inorga ´nica,

Reactions of Complex 1 with Monodentate