Reactions of [RuCp(L)(Lâ²)(CCPh)] (Cp = η5-C5H5; L = PPh3, Lâ²Â = P(OMe)3 1a; LLâ²Â = dppe = Ph2PCH2CH2PPh2 1b; L = PPh3, Lâ²Â = CNtBu 1c) with H(Ph)CC(CN)2 gave the cyclobutenyl complexes [RuCp(L)(Lâ²)CC(Ph)CH(Ph)C(CN)2}] 2a, 2b and 2c which readily transform to the butadienyl complexes [RuCp(L)(Lâ²)C[C(CN)2]C(Ph)CH(Ph)}] 3a, 3b and 3c, respectively. Thermolysis of 3a in benzene afforded the allylic complex [RuCpP(OMe)3}[η3-C[=C(CN)2]C(Ph)CH(Ph)}] 4 in high yield. Reaction of 4 with tBuNC gave [RuCpP(OMe)3}(CNtBu)[η1-C[C(CN)2]C(Ph)CH(Ph)}] 5. Treatment of 1a with Cl(Ph)CC(CN)2 afforded the neutral vinylidene phosphonate complex [RuCp(PPh3)P(O)(OMe)2}CC(Ph)C(Ph)C(CN)2}] 6. Reactions of 1b and 1c, both lacking phosphite ligands, with Cl(Ph)CC(CN)2 gave the cationic vinylidene complexes [RuCp(L)(Lâ²)CC(Ph)C(Ph)C(CN)2}]+ 7b and 7c, respectively. Treatment of 1a with ICH2CN afforded [RuCp(PPh3)P(OMe)3}CC(Ph)CH2CN}]I 8a. In the presence of acid complex 8a decomposes to give the acyl complex [RuCp(PPh3)P(OMe)3}(COCH2Ph)] 10. The structures of 3a, 4, 6 and the latter complex have been determined by single-crystal X-ray diffraction analysis.
RuCP(L)(Lâ²)(CCPh)] (CPÂ =Â Î-5-
C5H5; L = PPh3, Lâ²Â = P(OMe)3 1a; LLâ²Â = dppe = Ph2PCH2CH2PPh2 1b;LÂ=ÂPPh3,Lâ²Â= CNtBu 1c)与 H(Ph)CC(CN)2,得到
环丁烯基配合物[RuCP(L)(Lâ²)CC(Ph)CH(Ph)C(CN)2}] 2a、2b 和 2c,它们很容易转变为
丁二烯基配合物[RuCP(L)(Lâ²)C[C(CN)2]C(Ph)CH(Ph)}] 3a、3b 和 3c3a、3b 和 3c。3a 在苯中热解得到烯丙基络合物 [RuCPP(OMe)3}[δ-3-C[=C(CN)2]C(Ph)CH(Ph)}]4。4 的高产率。4 与 tBuNC 反应得到 [RuCPP(OMe)3}(CNtBu)[δ-1-C[C(CN)2]C(Ph)CH(Ph)}]5。5.用 Cl(Ph)CC(CN)2 处理 1a,可得到中性亚
乙烯基膦酸盐复合物 [RuCP(PPh3)P(O)(OMe)2}CC(Ph)C(Ph)C(CN)2}] 6。缺少
亚磷酸配体的 1b 和 1c 与 Cl(Ph)CC(CN)2 反应,分别得到阳离子亚
乙烯基络合物 [RuCP(L)(Lâ²)CC(Ph)C(Ph)C(CN)2}]+ 7b 和 7c。用 ICH2CN 处理 1a 得到[RuCP(PPh3)P(OMe)3}CC(Ph)CH2CN}]I 8a。在酸存在下,络合物 8a 分解生成酰基络合物 [RuCP(PPh3)P(OMe)3}(COCH2Ph)]10。通过单晶 X 射线衍射分析,确定了 3a、4、6 和后一种复合物的结构。