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首页> 外文期刊>Dalton transactions: An international journal of inorganic chemistry >Organometallic chemistry of ethynyl boronic acid MIDA ester, HC CB(O2CCH2)(2)NMe
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Organometallic chemistry of ethynyl boronic acid MIDA ester, HC CB(O2CCH2)(2)NMe

机译:乙炔基硼酸MIDA酯HC CB(O2CCH2)(2)NMe的有机金属化学

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The reactions of HC CBMIDA (BMIDA = B(O2CCH2)(2)NMe) with a range of ruthenium complexes afford the first isolated examples of sigma-alkynyl, sigma-alkenyl and vinylidene complexes bearing 4-coordinate boron substituents. Specifically, the reactions of HC CBMIDA with [RuH(S2CNR2)(CO)(PPh3)(2)] (R = Me, Et) and [Ru(CO)(2)(PPh3)(3)] afford the alkynyl complexes [Ru(C CBMIDA)(S2CNR2)(CO)(PPh3)(2)] and [RuH(C CBMIDA)-(CO)(2)(PPh3)(2)], the latter being converted to [Ru(C CBMIDA)Cl(CO)(2)(PPh3)(2)] on treatment with chloroform. With [RuCl(dppe)(2)]PF6 the vinylidene salt [RuCl(=C=CHBMIDA)(dppe)(2)]PF6 is obtained, which reacts with Et3N to afford the neutral alkynyl derivative [Ru(C=CBMIDA)Cl(dppe)(2)]. Hydrometallation of HC CBMIDA by [RuHCl(CO)(PPh3)(3)] affords the coordinatively unsaturated s-alkenyl complex [RuCl-(CH=CHBMIDA)(CO)(PPh3)(2)] which in turn reacts with CO, CNC6H2Me3-2,4,6, [Et2NH2][S2CNEt2] or K[HB(pz)(3)] (pz = pyrazol-1-yl) to afford the coordinatively saturated complexes [Ru(CH=CHBMIDA) Cl(CO)(2)(PPh3)(2)], [Ru(CH=CHBMIDA)Cl(CO)(CNC6H2Me3)(PPh3)(2)], [Ru(CH=CHBMIDA)(S2CNEt2)(CO)(PPh3)(2)] and [Ru(CH=CHBMIDA)(CO)(PPh3){HB(pz)(3)}]. In all cases, the transannular N -> B dative bond is retained in the BMIDA substituent.
机译:HC CBMIDA(BMIDA = B(O2CCH2)(2)NMe)与一系列钌配合物的反应提供了带有4位硼取代基的sigma-炔基,sigma-烯基和亚乙烯基配合物的第一个分离的实例。具体地说,HC CBMIDA与[RuH(S2CNR2)(CO)(PPh3)(2)](R = Me,Et)和[Ru(CO)(2)(PPh3)(3)]的反应提供炔基络合物[Ru(C CBMIDA)(S2CNR2)(CO)(PPh3)(2)]和[RuH(C CBMIDA)-(CO)(2)(PPh3)(2)],后者被转换为[Ru(C CBMIDA)Cl(CO)(2)(PPh3)(2)]用氯仿处理。用[RuCl(dppe)(2)] PF6得到亚乙烯基盐[RuCl(= C = CHBMIDA)(dppe)(2)] PF6,其与Et3N反应得到中性炔基衍生物[Ru(C = CBMIDA) Cl(dppe)(2)]。 [RuHCl(CO)(PPh3)(3)]对HC CBMIDA进行加氢金属化,可得到配位不饱和的s-烯基络合物[RuCl-(CH = CHBMIDA)(CO)(PPh3)(2)],进而与CO反应, CNC6H2Me3-2,4,6,[Et2NH2] [S2CNEt2]或K [HB(pz)(3)](pz =吡唑-1-基)得到配位饱和的络合物[Ru(CH = CHBMIDA)Cl(CO )(2)(PPh3)(2)],[Ru(CH = CHBMIDA)Cl(CO)(CNC6H2Me3)(PPh3)(2)],[Ru(CH = CHBMIDA)(S2CNEt2)(CO)(PPh3) (2)]和[Ru(CH = CHBMIDA)(CO)(PPh3){HB(pz)(3)}]。在所有情况下,BMIDA取代基均保留跨环的N→B键。

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