Treatment of tetranuclear [RuF(μ-F)(CO)3]4 (1) with the free N-heterocyclic carbenes (NHCs), IMes (1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene) and IPr (1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene), followed by work-up in carbon tetrachloride leads to fluoride-bridge cleavage in 1 and the formation of the mononuclear octahedral complexes cis,cis,trans-[RuF2(CO)2(NHC)2] [NHC = IMes (2a), IPr (2b)], respectively. Complexes 2a and 2b can also be obtained by interaction of 1 with the corresponding imidazolium chloride, [-N(Ar)CHN(Ar)CHCH-]Cl (Ar = 2,4,6-Me3C6H2, 2,6-i-Pr2C6H3), in the presence of KOtBu. However, extension of this latter base-assisted approach to [-N(Ar)CHN(Ar)CHCH-]Cl (Ar = 2,6-Me2C6H3, 2,4,6-i-Pr3C6H2) results in halide exchange with the work-up solvent (CCl4) to generate cis,cis,trans-[RuCl2(CO)2(IMe)2] (3) and dinuclear [RuCl(μ-Cl)(CO)2(ITPr)]2 (4), respectively. Reaction of 2a with gaseous BF3 in dichloromethane and subsequent carbonylation affords in high yield monocationic [Ru(FBF3)(CO)3(IMes)2](BF4) (5), while with 2b, BF3 addition alone results in solvent exchange to yield dinuclear monocationic [Ru2(μ-Cl)3(CO)4(IPr)2](BF4)/(F) (6). Conversely, interaction of 2a and 2b with BF3·OEt2 in acetonitrile furnishes dicationic cis,cis,trans-[Ru(CO)2(NCMe)2(NHC)2](BF4)2 [NHC = IMes (7a), IPr (7b)]; in the case of 7acarbonylation gives [Ru(CO)4(IMes)2](B2F7)2 (8). Single crystal X-ray structures are presented for 3, 4, 5, 6 and 8.
将四核 [RuF(μ-F)(CO)3]4 (1) 与自由N-杂环卡宾 (NHCs) IMes (1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene) 和 IPr (1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene) 处理后在
四氯化碳中进行后处理,导致1中的
氟桥断裂,形成单核八面体配合物 cis,cis,trans-[RuF2(CO)2(NHC)2] [NHC = IMes (2a), IPr (2b)]。配合物2a和2b也可以通过将1与相应的
咪唑鎓
氯化物 [-N(Ar)CHN(Ar)CHCH-]Cl (Ar = 2,4,6-Me3C6H2, 2,6-i-Pr2C6H3) 在KOtBu存在下相互作用获得。然而,将这种后者的碱辅助方法扩展到[-N(Ar)CHN(Ar)CHCH-]Cl (Ar = 2,6-Me2C6H3, 2,4,6-i-Pr3C6H2) 会导致与工作溶剂 (
CCl4) 的卤化物交换,生成 cis,cis,trans-[RuCl2(CO)2(IMe)2] (3) 和二核 [RuCl(μ-Cl)(CO)2(ITPr)]2 (4)。将2a与气态
BF3在
二氯甲烷中反应,经过后续的羰基化反应可高产率获得单阳离子 [Ru(F )(CO)3(IMes)2](
BF4) (5),而与2b反应时,单独添加 则导致溶剂交换,生成二核单阳离子 [Ru2(μ-Cl)3(CO)4(IPr)2]( )/(F) (6)。相反,在
乙腈中将2a和2b与 ·OEt2相互作用,可以产生二阳离子 cis,cis,trans-[Ru(CO)2(NCMe)2(NHC)2]( )2 [NHC = IMes (7a), IPr (7b)];在7a的情况下,羰基化反应生成 [Ru(CO)4(IMes)2](B2F7)2 (8)。对3、4、5、6和8的单晶X射线结构进行了展示。