Chemical Reactivity and Electrochemistry of Metal鈥揗etal-Bonded Zincocenes
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- 作者：Mario Carrasco ; Riccardo Peloso ; Irene Resa ; Amor Rodri虂guez ; Luis Sa虂nchez ; Eleuterio A虂lvarez ; Celia Maya ; Rafael Andreu ; Juan Jose虂 Calvente ; Agusti虂n Galindo ; Ernesto Carmona
- 刊名：Inorganic Chemistry
- 出版年：2011
- 出版时间：July 4, 2011
- 年：2011
- 卷：50
- 期：13
- 页码：6361-6371
- 全文大小：1124K
- 年卷期：v.50,no.13(July 4, 2011)
- ISSN：1520-510X
文摘
Attempts to prepare mixed-ligand zinc鈥搝inc-bonded compounds that contain bulky C5Me5 and terphenyl groups, [Zn2(C5Me5)(Ar鈥?], lead to disproportionation. The resulting half-sandwich Zn(II) complexes [(畏5-C5Me5)ZnAr鈥瞉 (Ar鈥?= 2,6-(2,6-iPr2C6H3)2-C6H3, 2; 2,6-(2,6-Me2C6H3)2-C6H3, 3) can also be obtained from the reaction of [Zn(C5Me5)2] with the corresponding LiAr鈥? In the presence of pyr-py (4-pyrrolidinopyridine) or DBU (1,8-diazabicyclo[5.4.0]undec-7-ene), [Zn2(畏5-C5Me5)2] reacts with C5Me5OH to afford the tetrametallic complexes [Zn2(畏5-C5Me5)L(渭-OC5Me5)]2 (L = pyr-py, 6; DBU, 8), respectively. The bulkier terphenyloxide ArMesO鈥?/sup> group (ArMes = 2,6-(2,4,6-Me3C6H2)2-C6H3) gives instead the dimetallic compound [Zn2(畏5-C5Me5)(OArMes)(pyr-py)2], 7, that features a terminal Zn鈥揙ArMes bond. DFT calculations on models of 6鈥?b>8 and also on the Zn鈥揨n-bonded complexes [Zn2(畏5-C5H5)(OC5H5)(py)2] and [(畏5-C5H5)ZnZn(py)3]+ have been performed and reveal the nonsymmetric nature of the Zn鈥揨n bond with lower charge and higher participation of the s orbital of the zinc atom coordinated to the cyclopentadienyl ligand with respect to the metal within the pseudo-ZnL3 fragment. Cyclic voltammetric studies on [Zn2(畏5-C5Me5)2] have been also carried out and the results compared with the behavior of [Zn(C5Me5)2] and related magnesium and calcium metallocenes.