Abstract
The ligand 1,4-bis[4-(diphenylphosphino)butyl]-2,3,5,6-tetramethylbenzene, 3, was used to synthesize a mononuclear Rh(II) complex [(η1:η6:η1-1,4-bis[4- (diphenylphosphino)butyl]-2,3,5,6-tetramethylbenzene)Rh] [PF6]2, 6+, in a two-legged piano-stool geometry. The structural and electronic properties of this novel complex including a single-crystal EPR analysis are reported. The complex can be cleanly interconverted with its Rh(I) form, allowing for a comparison of the structural properties and reactivity of both oxidation states. The Rh(I) form 6 reacts with CO, tert-butyl isocyanide, and acetonitrile to form a series of 15-membered mononuclear cyclophanes [(η1:η1-1,4-bis[4- (diphenylphosphino)butyl]-2,3,5,6-tetramethylbenzene)Rh(CO)3][PF6] (8), [(η1:η1-1,4-bis[4-(diphenylphosphino)butyl]-2, 3,5,6-tetramethylbenzene)Rh(CNC(CH3)3)2] [PF6] (10), and [η1:η1-1,4-bis[4-(diphenylphosphino)butyl]-2, 3,5,6tetramethylbenzene)Rh(CO)(CH3CN)][PF6] (11). The Rh(II) complex 6+ reacts with the same small molecules, but over shorter periods of time, to form the same Rh(I) products. In addition, a model two-legged piano-stool complex [(η1:η6:η1-1,4-bis[3- (diphenylphosphino)propoxy] -2,3,5,6-tetramethyl benzene) Rh][B(C6F5)4], 5, has been synthesized and characterized for comparison purposes. The solid-state structures of complexes 5, 6, 6+, and 11 are reported. Structure data for 5: triclinic; P1-; a = 10.1587(7) Å; b = 11.5228(8) Å; c = 17.2381(12) Å; α = 96.4379(13)°; β = 91.1870(12)°; γ = 106.1470(13)°; Z= 2. 6: triclinic; P1- a = 11.1934(5) Å; b = 12.4807(6) Å; c = 16.1771(7) Å; α = 81.935(7)°; β = 89.943(1)°; γ = 78.292(1)°; γ = 78.292(1)°; Z = 2. 6+: monoclinic; P2(1)/n; a = 11.9371(18) Å; b = 32.401(5) Å; c = 12.782(2) Å; β = 102.890(3)°; Z = 4. 11: triclinic; P1-; a = 13.5476(7) Å; b = 13.8306(7) Å; c = 14.9948(8) Å; α = 74.551(1)°; β = 73.895(1)°; γ = 66.046(1)°; Z = 2.
Original language | English (US) |
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Pages (from-to) | 3245-3255 |
Number of pages | 11 |
Journal | Inorganic chemistry |
Volume | 42 |
Issue number | 10 |
DOIs | |
State | Published - May 19 2003 |
ASJC Scopus subject areas
- Inorganic Chemistry
- Physical and Theoretical Chemistry
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CCDC 189166: Experimental Crystal Structure Determination
Dixon, F. M. (Creator), Masar III, M. S. (Contributor), Doan, P. E. (Creator), Farrell, J. R. (Creator), Mirkin, C. A. (Creator), Incarvito, C. D. (Creator), Zakharov, L. N. (Creator) & Rheingold, A. L. (Creator), Cambridge Crystallographic Data Centre, 2003
DOI: 10.5517/cc6bv4h, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/cc6bv4h&sid=DataCite
Dataset
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CCDC 173489: Experimental Crystal Structure Determination
Dixon, F. M. (Creator), Farrell, J. R. (Creator), Doan, P. E. (Creator), Williamson, A. (Creator), Weinberger, D. A. (Creator), Mirkin, C. A. (Creator), Stern, C. (Creator), Incarvito, C. D. (Creator), Liable-Sands, L. M. (Creator), Zakharov, L. N. (Creator) & Rheingold, A. L. (Creator), Cambridge Crystallographic Data Centre, 2002
DOI: 10.5517/cc5tjfx, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/cc5tjfx&sid=DataCite
Dataset
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CCDC 175054: Experimental Crystal Structure Determination
Dixon, F. M. (Creator), Farrell, J. R. (Creator), Doan, P. E. (Creator), Williamson, A. (Creator), Weinberger, D. A. (Creator), Mirkin, C. A. (Creator), Stern, C. (Creator), Incarvito, C. D. (Creator), Liable-Sands, L. M. (Creator), Zakharov, L. N. (Creator) & Rheingold, A. L. (Creator), Cambridge Crystallographic Data Centre, 2002
DOI: 10.5517/cc5w4x2, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/cc5w4x2&sid=DataCite
Dataset