ORGANOMETALLIC OXIDES - OXIDATION OF [(ETA-C5ME5)MO(CO)2]2 WITH O2 TO FORM SYN-[(ETA-C5ME5)MOCL]2(MU-CL)2(MU-O), SYN-[(ETA-C5ME5)MOCL]2(MU-CL)(MU-CO3H)(MU-O), AND [C5ME5O][(ETA-C5ME5)MO6O18]
ORGANOMETALLIC OXIDES - OXIDATION OF [(ETA-C5ME5)MO(CO)2]2 WITH O2 TO FORM SYN-[(ETA-C5ME5)MOCL]2(MU-CL)2(MU-O), SYN-[(ETA-C5ME5)MOCL]2(MU-CL)(MU-CO3H)(MU-O), AND [C5ME5O][(ETA-C5ME5)MO6O18]
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DOI：
10.1021/om00046a045
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发表时间：
1992-10-01
期刊：
影响因子：
2.8
通讯作者：
CHEN, JH
中科院分区：
文献类型：
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作者：
BOTTOMLEY, F;CHEN, JH
[（eta-C5 Me 5）Mo（CO）2]2在CHCl 3中通过空气氧化得到[CrMe 5 O][（eta-C5 Me 5）Mo 6 O 18]，这是一个前所未有的反应，其中氧原子被插入C5环中。氧化反应还得到了[（eta-C5 Me 5）Mo（O）2]2（μ-O）和（eta-C5 Me 5）MoCl（O）2。[C_5Me_5 O][（eta-C_5 Me_5）Mo_6 O_（18）]的结构经X射线衍射测定（正交晶系，a = 15.971（1）埃，B = 16.825（1）埃，c = 23.597（1）埃，Pcab空间群，Z = 8，R '= 0.051）。阴离子是经典的{[Mo（O）（mu-O）2]6（mu 6-O）}2-的衍生物，其中末端氧已被eta-C5 Me 5取代。Mo=O的强反式效应表现为其自身穿过Mo 6（mu 6-O）八面体到Mo-（eta-C5 Me 5）单元。[（eta-C_5 Me_5）Mo（CO）_2]_2在氧气存在下辐照得到了syn-[（eta-C_5 Me_5）MoCl]_2（mu-Cl）_2（mu-O）和syn-[（eta-C_5 Me_5）MoCl]_2（mu-Cl）（mu-CO_3 H）（mu-O），其结构经X射线衍射测定。syn-[（eta-C5 Mer）MoCl]2（mu-Cl）2（mu-O）为正交晶系，a = 8.581（7）埃，B = 39.610（6）埃，c = 56.650（8）埃，空间群F2 dd，Z = 32，R = 0.195。[（eta-C5 Me 5）MoCl]2（mu-Cl）（mu-CO 3 H）（mu-O）为单斜晶系，a = 8.451（8）埃，B = 28.771（16）埃，c = 10.925（14）埃，β = 107.2（10）度，空间群P2（1）/c，Z = 4，R = 0.073。这些抗磁性双核化合物具有长的Mo-Mo距离（分别为2.72和2.80埃）。扩展的Huckel计算表明，Mo-Mo键很少，18电子规则所要求的正式Mo-Mo描述是不正确的。
Oxidation of [(eta-C5Me5)Mo(CO)2]2 by air in CHCl3 gave [CrMe5O][(eta-C5Me5)Mo6O18], in an unprecedented reaction in which an oxygen atom was inserted into a C5 ring. The previously reported complexes [(eta-C5Me5)Mo(O)2]2(mu-O) and (eta-C5Me5)MoCl(O)2 were also obtained from the oxidation. The structure of [C5Me5O][(eta-C5Me5)Mo6O18] has been determined by X-ray diffraction (orthorhombic, a = 15.971 (1) angstrom, b = 16.825 (1) angstrom, c = 23.597 (1) angstrom, space group Pcab, Z = 8, R'= 0.051). The anion is a derivative of the Classic {[Mo(O)(mu-O)2]6(mu6-O)}2-, in which a terminal oxygen has been replaced by eta-C5Me5. The strong trans effect of Mo=O manifests itself across the Mo6(mu6-O) octahedron to the Mo-(eta-C5Me5) unit. Irradiation of [(eta-C5Me5)Mo(CO)2]2 in the presence of O2 gave syn-[(eta-C5Me5)MoCl]2(mu-Cl)2(mu-O) and syn-[(eta-C5Me5)MoCl]2(mu-Cl)(mu-CO3H)(mu-O), whose structures have been determined by X-ray diffraction. syn-[(eta-C5Mer)MoCl]2(mu-Cl)2(mu-O) is orthorhombic, with a = 8.581 (7) angstrom, b = 39.610 (6) angstrom, c = 56.650 (8) angstrom, space group F2dd, Z = 32, and R = 0.195. [(eta-C5Me5)MoCl]2(mu-Cl)(mu-CO3H)(mu-O) is monoclinic, with a = 8.451 (8) angstrom, b = 28.771 (16) angstrom, c = 10.925 (14) angstrom, beta = 107.2 (10)-degrees, space group P2(1)/c, Z = 4, and R = 0.073. These diamagnetic dinuclear compounds have long Mo-Mo distances (2.72 and 2.80 angstrom, respectively). Extended Huckel calculations show that there is very little Mo-Mo bonding, and the formal Mo-Mo description required by the 18-electron rule is incorrect.