The reaction of Os3(CO)12 with triphos {MeC(CH2PPh2)3}: A case of multiple C-P and C-H bond activations

被引：0
|
作者：
Jung, Jade Y. [1 ]
Marolf, David M. [1 ]
Yoon, Soo Hun [1 ]
Powell, Gregory L. [1 ]
Yang, Li [2 ]
Nesterov, Vladimir N. [2 ]
Richmond, Michael G. [2 ]
机构：
[1] Abilene Christian Univ, Dept Chem & Biochem, Abilene, TX 79699 USA
[2] Univ North Texas, Dept Chem, Denton, TX 76203 USA
来源：
JOURNAL OF ORGANOMETALLIC CHEMISTRY | 2017年 / 849-850卷
关键词：
Triosmium carbonyl cluster; Triphos ligand; C-P bond cleavage; C-H bond activation; X-ray crystal structure; SET MODEL CHEMISTRY; TRIOSMIUM CLUSTERS; ORTHO-METALATION; DFT EVALUATION; TOTAL ENERGIES; LIGAND; HYDRIDES; COMPLEXES;
D O I：
10.1016/j.jorganchem.2017.03.039
中图分类号：
O61 [无机化学];
学科分类号：
070301 ; 081704 ;
摘要：
The reaction of Os-3(CO)(12) with the tripodal ligand 1,1,1-tris(diphenylphosphinomethyl)ethane, triphos, results in the formation of the 48e trinuclear cluster complex Os-3[mu-Ph2PCH2C(Me)(CH2PPh) CH2PC6H4](CO)(7)(eta(1)-Ph). This new complex has been characterized by X-ray crystallography as well as by IR and NMR spectroscopy. The activation of the triphos ligand to yield the novel 9e donor ligand Ph2PCH2C(Me)(CH2PPh)CH2PC6H4 is unprecedented. The triphos ligand does not cap the triangular Os-3 face; instead, the three phosphorus atoms are coordinated to only two of the metal atoms with the remaining osmium atom coordinated by an ortho-metalated aryl group. The triphos ligand is also transformed in several ways. Two C-P bonds are cleaved during the reaction, yielding an eta(1) phenyl ligand in the product and free benzene. The bonding in 1 has been examined by electronic structure calculations. (C) 2017 Elsevier B.V. All rights reserved.
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页码：125 / 129
页数：5
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