Synthesis and Insertion Behavior of Carbonylhydridonitrosyltris(trimethylphosphine)tungsten(0)
Synthesis and Insertion Behavior of Carbonylhydridonitrosyltris(trimethylphosphine)tungsten(0)
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羰基氢化亚硝酰基三(三甲基膦)钨(0)的合成及插入行为
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发表时间：
2001
期刊：
影响因子：
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通讯作者：
H. Berke
中科院分区：
文献类型：
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作者：
Jürgen Höck;H. Jacobsen;H. Schmalle;G. Artus;T. Fox;J. I. Amor;and Frank Bäth;H. Berke
介绍了合成mer-W(CO)(H)(NO)(PMe3)3(4)的两种途径，从mer-W(Cl)(CO)(NO)(PMe3)3(1)或硼氢化物络合物mer-W(η - 1- bh4)(CO)(NO)(PMe3)3(3)开始。对4发生插入反应的倾向进行了研究。4与苯甲醛、丙醛、戊醛、二苯甲酮、苯乙酮和丙酮反应生成相应的醇氧配合物mer-W(CO)(NO)(PMe3)3(OCHR ' R ' ')(R ' = H, R ' ' = Ph (5a))；R ' ' = H, R ' ' = CH2CH2CH3 (5b)；R ' ' = H, R ' ' = CH2C(CH3)3 (5c)；R ' = Ph, R ' ' = Ph (5d)；R ' = CH3, R ' ' = Ph (5e)；R ' ' = CH3, R ' ' = CH3 (5f))CO2的插入产生形成o络合物mer-W(CO)(NO)(OCHO)(PMe3)3(6)。4与CO反应导致PMe3立即损失，生成反式，反式w (CO)2(H)(NO)(PMe3)2。Fe(CO)5和Re2(CO)10以可逆方式插入到4的W−H键中，形成可分离的μ-甲酰基配合物mer-W(CO)(NO)(PMe3)3[(μ-OCH)Fe(CO)4] （7a）和mer-W(CO)(NO)(PMe3)3[(μ-OCH)Re2(CO)9] （7b）作为平衡组分。b…
Two routes for the synthesis of mer-W(CO)(H)(NO)(PMe3)3 (4) are described, starting from mer-W(Cl)(CO)(NO)(PMe3)3 (1) or the borohydride complex mer-W(η1-BH4)(CO)(NO)(PMe3)3 (3). The propensity of 4 to undergo insertion reactions has been investigated. 4 reacts with benzaldehyde, propionaldehyde, pivalaldehyde, benzophenone, acetophenone, and acetone to afford the corresponding alkoxide complexes mer-W(CO)(NO)(PMe3)3(OCHR‘R‘ ‘) (R‘ = H, R‘ ‘ = Ph (5a); R‘ = H, R‘ ‘ = CH2CH2CH3 (5b); R‘ = H, R‘ ‘ = CH2C(CH3)3 (5c); R‘ = Ph, R‘ ‘ = Ph (5d); R‘ = CH3, R‘ ‘ = Ph (5e); R‘ = CH3, R‘ ‘ = CH3 (5f)). Insertion of CO2 yields the formato-O complex mer-W(CO)(NO)(OCHO)(PMe3)3 (6). Reaction of 4 with CO leads to immediate loss of PMe3 and formation of trans,trans-W(CO)2(H)(NO)(PMe3)2. In a reversible way Fe(CO)5 and Re2(CO)10 insert into the W−H bond of 4, affording the isolable μ-formyl complex mer-W(CO)(NO)(PMe3)3[(μ-OCH)Fe(CO)4] (7a) and mer-W(CO)(NO)(PMe3)3[(μ-OCH)Re2(CO)9] (7b) as an equilibrium constituent. For b...