Synthesis, structure, and reactivity of tungsten acetylide-germylene complexes

Hiroyuki Sakaba, Yasuhiro Arai, Kensei Suganuma, Eunsang Kwon

研究成果: Article査読

8 被引用数 (Scopus)


The novel acetylide-germylene complexes Cp*(CO) 2W(GePh2)(CCR) (7a, R = SiMe3; 7b, R = CMe 3) were synthesized by the reactions of Cp*(CO) 2W(NCMe)Me with Ph2HGeCî - CR (R = SiMe3, CMe3). X-ray crystal analysis of 7a revealed significantly increased germylene-tungsten and decreased germylene-acetylide interactions in comparison to the corresponding interactions in the previously reported acetylide-silylene complex Cp*(CO)2W(SiPh2)(CCSiMe3) (1). Complexes 7a,b reacted with acetone to give the six-membered cyclic vinylidene complexes Cp*(CO)2W=C=C(R)CMe2OGePh2 (8a, R = SiMe3; 8b, R = CMe3) by acetone insertion reaction, similar to the case of 1 affording Cp*(CO)2W=C=C(SiMe 3)CMe2OSiPh2 (2). In the presence of 4-(dimethylamino)pyridine (DMAP), complexes 8a,b gave trans- and cis-DMAP-stabilized germylene acetylide complexes Cp*(CO) 2W(GePh2·DMAP)(CCR) (trans- and cis-9a, R = SiMe3; trans- and cis-9b, R = CMe3) and acetone, showing a reactivity different from that of the silicon analogue 2. Complexes cis-9a,b were isolated as crystals from the reaction of 7a,b with DMAP and formed mixtures with trans-9a,b in solutions, respectively. A mixture of cis- and trans-9a reacted with acetone to form an equilibrium mixture with 8a and DMAP. The reactivity of 7a,b toward Me3COH was also investigated to reveal the formation of the vinylidene complexes Cp*(CO)2W{GePh 2(OCMe3)}=C=CHR (10a, R = SiMe3; 10b, R = CMe3); 10a is equilibrated with 7a and Me3COH, whereas 10b is further converted to the carbyne complex Cp*(CO)2Wî - CCH(CMe3){GePh2(OCMe3)} (11).

出版ステータスPublished - 2013 9月 23

ASJC Scopus subject areas

  • 物理化学および理論化学
  • 有機化学
  • 無機化学


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