Ground-State and Excited-State Structures of Tungsten–Benzylidyne Complexes

• Published in: Inorganic chemistry 2012-05, Vol.51 (10), p.5660-5670
• Main Authors: Lovaasen, Benjamin M, Lockard, Jenny V, Cohen, Brian W, Yang, Shujiang, Zhang, Xiaoyi, Simpson, Cheslan K, Chen, Lin X, Hopkins, Michael D
• Format: Article
• Language: English
• Subjects: ABSORPTION; ABSORPTION SPECTROSCOPY; BOND LENGTHS; CRYSTAL STRUCTURE; CRYSTALLOGRAPHY; ELECTRON TRANSFER; ELONGATION; EXCITED STATES; FUNCTIONALS; GROUND STATES; MATERIALS SCIENCE; MOLECULAR STRUCTURE; TRANSIENTS; TRIPLETS
• ISSN: 0020-1669; 1520-510X
• DOI: 10.1021/ic202622s

The molecular structure of the tungsten–benzylidyne complex trans-W(CPh)(dppe)2Cl (1; dppe = 1,2-bis(diphenylphosphino)ethane) in the singlet (d xy )2 ground state and luminescent triplet (d xy )1(π*(WCPh))1 excited state (1*) has been studied using X-ray transient absorption spectroscopy, X-ray crystallography, and density functional theory (DFT) calculations. Molecular-orbital considerations suggest that the W–C and W–P bond lengths should increase in the excited state because of the reduction of the formal W–C bond order and decrease in W→P π-backbonding, respectively, between 1 and 1*. This latter conclusion is supported by comparisons among the W–P bond lengths obtained from the X-ray crystal structures of 1, (d xy )1-configured 1 + , and (d xy )2 [W(CPh)(dppe)2(NCMe)]+ (2 +). X-ray transient absorption spectroscopic measurements of the excited-state structure of 1* reveal that the W–C bond length is the same (within experimental error) as that determined by X-ray crystallography for the ground state 1, while the average W–P/W–Cl distance increases by 0.04 Å in the excited state. The small excited-state elongation of the W–C bond relative to the M–E distortions found for M(E)L n (E = O, N) compounds with analogous (d xy )1(π*(ME))1 excited states is due to the π conjugation within the WCPh unit, which lessens the local W–C π-antibonding character of the π*(WCPh) lowest unoccupied molecular orbital (LUMO). These conclusions are supported by DFT calculations on 1 and 1*. The similar core bond distances of 1, 1 + , and 1* indicates that the inner-sphere reorganization energy associated with ground- and excited-state electron-transfer reactions is small.