Aromaten(phosphan)metall‐Komplexe, I. Die Vorstufen zur Synthese der Metall‐Basen ArM(PR₃)₂ und ArM(PR₃)L (M = Ru, Os)

Abstract

Die halogen‐verbrückten Verbindungen [ArRuX2]2 (AR = C6H6, p‐Cymol, C6Me6; X = Cl, und AR = C6H6; X = I) und [C6H6OsI2]2 reagieren mit Lewis‐Basen L wie z. B. CO, tertiären Phosphanen oder Trimethylphosphit zu den einkernigen Komplexen ArMX2(L) (1 – 9). Aus diesen erhält man (für AR = C6H6) mit AgPF6 in Aceton (ac) die Verbindungen [C6H6RuCl(L)(ac)]PF6 (10 – 12) und [(C6H6ML)2(μ‐X)2(PF6)2](C6H6ML)[2(μ‐X)2](PF6) 2 (13 – 20). Bei der Reaktion von [ArRuX2]2 und [C6H6OsI2]2 mit einem Überschuß an PR3 und NH4PF6 in Methanol entstehen die Komplexe [ArMX(PR3)2]PF6 (21 – 29). Die Synthese der analogen Verbindungen [ArMX(PR3)L]PF6 (30 – 39) gelingt durch Umsetzung von ArMX2(L) mit PR3 und NH4PF6 in Methanol. Die Osmium‐Komplexe [C6H6OsI(L)2]PF6 (40, 41) und [C6H6OsI(PR3)CO]PF6 (42, 43) werden aus [(C6H6OsL)2(μ‐I)2(PF6)2] und L bzw. aus C6H6OsI2(PR3) und CO in Gegenwart von AgPF6 dargestellt.

Activation of Mononuclear Arene Ruthenium Complexes for Catalytic Propargylation Directly with Propargyl Alcohols

“…[21] In fact, 6a/6b are more readily prepared from the parent complexes 3a/3b on addition of carbon monoxide. The question is whether these saturated complexes could be related or not to the catalytically active species.…”

“…Chemicals were obtained commercially and used as supplied, except for the alkynols 1d and 1e. [30] Complexes 2a and 2b, [21] and 3a and 3b, [31] were prepared according to reported methods. Complexes 6a and 6b were obtained as described by Werner et al, [21] but using AgOTf as chloride abstractor.…”

“…[30] Complexes 2a and 2b, [21] and 3a and 3b, [31] were prepared according to reported methods. Complexes 6a and 6b were obtained as described by Werner et al, [21] but using AgOTf as chloride abstractor. The formation of compounds 5a, 5b, 6a and 6b, observed by low temperature [ 10] NMR spectra were recorded on Bruker AM 3000 WB and DPX 200 spectrometers in deuterated solvents.…”

Mononuclear Ruthenium Catalysts for the Direct Propargylation of Heterocycles with Propargyl Alcohols

“…Mixed phosphine-carbonyl arene-ruthenium complexes have already been reported by Werner et al, [16] and complexes 10 and 13 can be more readily prepared from the parent complexes 4 and 5 on addition of carbon monoxide. Surprisingly, the saturated complexes 10 and 13 also catalyse the propargylation of furan and 2-methylfuran by alkynol 1 and require a remarkable shorter reaction time.…”

“…Chemicals were obtained commercially and used as supplied. (10), PPh 3 (13)] were obtained as described by Werner et al, [16] but using AgOTf as chloride abstractor. NMR spectra were recorded on Bruker AM 3000 WB and DPX 200 spectrometers in deuterated solvents.…”