approximately 7). Addition of HOSO(2)CF(3) to solutions of 2a results in protonation at the metal and formation of the cationic rhenium hydride [trans,trans-ReH(CO)(2)(NO)(PPh(3))(2)(+)][SO(3)CF(3)(-)] (4) in 74% yield; the deuteride [trans,trans-Re((2)H)(CO)(2)(NO)(PPh(3))(2)(+)][SO(3)CF(3)(-)] (4-d) was analogously prepared from (2)HOSO(2)CF(3). 4 crystallized from CH(2)Cl(2)/Et(2)O solution in the orthorhombic
盐酸和
三氟甲磺酸与五配位亚
硝酰基配合物trans-Re(CO)(2)(NO)(PR(3))(2)的反应(2a,R = Ph; 2b,R = Cy)调查。无
水HCl与2的反应导致亚
硝酰基
配体的正式质子化并向
金属中添加
氯化物,得到中性亚
硝酰络合物顺式,反式-ReCl(CO)(2)(NH = O)(PR(3)) (2)(3a,R = Ph; 3b,R = Cy)。当碱强度适当时(pK(b)约为7),布朗斯台德碱与3a或3b的反应导致3到2的纯净转化。将HOSO(2)CF(3)添加到2a溶液中会导致
金属质子化并形成阳离子氢化[trans,trans-ReH(CO)(2)(NO)(PPh(3))(2 )(+)] [SO(3)CF(3)(-)](4),产率74%;
氘代[反式,反式Re((2)H)(CO)(2)(NO)(PPh(3))(2)(+)] [SO(3)CF(3)(-)](4-d)为由(2)HO