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.

引用

页码：125 / 129

页数：5

共 37 条

[11] ELECTRONIC-STRUCTURE AND BONDING IN METHYL(PENTACARBONYL)MANGANESE AND PERFLUOROMETHYL(PENTACARBONYL)MANGANESE
HALL, MB
FENSKE, RF
[J]. INORGANIC CHEMISTRY, 1972, 11 (04) : 768 - &
[12] Close Correlation between Metal Oxidation States and Molecular Structures in a Cobalt-Gold Multinuclear Coordination System with Mixed D-Penicillaminate and Tripodal Triphosphine
Hashimoto, Yuji
Yoshinari, Nobuto
Matsushita, Natsuko
Konno, Takumi
[J]. EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, 2014, (22) : 3474 - 3478
[13] DFT Investigation of the Mechanism of Phosphine-Thioether Isomerization in the Triosmium Cluster Os3(CO)10(Ph2PCH2CH2SMe): Migratory Preference for the Formation of an Edge-Bridged Thioether versus a Phosphine Moiety
Hrovat, David A.
Nordlander, Ebbe
Richmond, Michael G.
[J]. ORGANOMETALLICS, 2012, 31 (18) : 6608 - 6613
[14] Ortho-Metalation Dynamics and Ligand Fluxionality in the Conversion of Os3(CO)10(dppm) to HOs3(CO)8[μ-PhP(C6H4-μ2,η1)CH2PPh2]: Experimental and DFT Evidence for the Participation of Agostic C-H and π-Aryl Intermediates at an Intact Triosmium Cluster
Huang, Shih-Huang
Keith, Jason M.
Hall, Michael B.
Richmond, Michael G.
[J]. ORGANOMETALLICS, 2010, 29 (18) : 4041 - 4057
[15] Microwave-induced dppm ligand substitution in triosmium clusters: Structural and DFT evaluation of Os3 clusters containing multiply activated dppm ligands through cyclometalation, ortho metalation, and P-C bond cleavage
Jung, Jade Y.
Kempe, David K.
Yoon, Soo Hun
Gwini, Nigel
Fikes, Audrey G.
Marolf, David M.
Parker, Michelle L.
Johnstone, James E.
Powell, Gregory L.
Yang, Li
Nesterov, Vladimir N.
Richmond, Michael G.
[J]. JOURNAL OF ORGANOMETALLIC CHEMISTRY, 2016, 813 : 15 - 25
[16] DEVELOPMENT OF THE COLLE-SALVETTI CORRELATION-ENERGY FORMULA INTO A FUNCTIONAL OF THE ELECTRON-DENSITY
LEE, CT
YANG, WT
PARR, RG
[J]. PHYSICAL REVIEW B, 1988, 37 (02): : 785 - 789
[17] 2-[(Diphenylphosphino)methyl]-6-methylpyridine (PN) coordination chemistry at triosmium clusters: Regiospecific ligand activation and DFT evaluation of the isomeric Os3(CO)10(PN) clusters
Lin, Chen-Hao
Nesterov, Vladimir N.
Richmond, Michael G.
[J]. JOURNAL OF ORGANOMETALLIC CHEMISTRY, 2013, 744 : 24 - 34
[18] New Wind in Old Sails: Novel Applications of Triphos-based Transition Metal Complexes as Homogeneous Catalysts for Small Molecules and Renewables Activation
Mellone, Irene
Bertini, Federica
Gonsalvi, Luca
Guerriero, Antonella
Peruzzini, Maurizio
[J]. CHIMIA, 2015, 69 (06) : 331 - 338
[19] A COMPLETE BASIS SET MODEL CHEMISTRY .3. THE COMPLETE BASIS SET-QUADRATIC CONFIGURATION-INTERACTION FAMILY OF METHODS
PETERSSON, GA
TENSFELDT, TG
MONTGOMERY, JA
[J]. JOURNAL OF CHEMICAL PHYSICS, 1991, 94 (09) : 6091 - 6101
[20] A COMPLETE BASIS SET MODEL CHEMISTRY .2. OPEN-SHELL SYSTEMS AND THE TOTAL ENERGIES OF THE 1ST-ROW ATOMS
PETERSSON, GA
ALLAHAM, MA
[J]. JOURNAL OF CHEMICAL PHYSICS, 1991, 94 (09) : 6081 - 6090

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