Ambidentate coordination of the tripyridyl ligands 2,2′:6',2"-terpyridyl, tris(2-pyridyl)-amine, tris(2-pyridyl)methane and tris(2-pyridyl)phosphine to carbonylrhenium centres: structural and spectroscopic studies

Anderson, Peter A., Keene, F. Richard, Horn, Ernst, and Tiekink, Edward R.T. (1990) Ambidentate coordination of the tripyridyl ligands 2,2′:6',2"-terpyridyl, tris(2-pyridyl)-amine, tris(2-pyridyl)methane and tris(2-pyridyl)phosphine to carbonylrhenium centres: structural and spectroscopic studies. Applied Organometallic Chemistry, 4 (5). pp. 523-533.

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Abstract

The reactions of [Re(CO)₅Cl] with the ligands tpy (2,2':6',2"-terpyridine), py₃N {tris(2-pyridyl)-amine}, py₃CH {tris(2-pyridyl)methane}, and py₃P {tris(2-pyridyl)phosphine} in toluene solution realize compounds with the general formulation [Re(ligand)(CO)₃Cl] in which the tripyridyl ligands are bidentate. X-ray structural determinations of fac-[Re(typ)(CO)₃Cl].H₂O and fac-[Re(py₃N)(CO)₃Cl] confirm these assignments. [Re(tpy)(CO)₃Cl].H₂O (C₁₈H₁₃ClN₃O₄Re) is monoclinic, space group P21/n, with cell dimensions a = 7.432(2) Å, b = 17.016(4) Å, c = 14.466(2) Å, β = 93.51(2)°, and Z = 4; full-matrix least-squares refinement on 2435 reflections with I ⩾ 2.5σ(I) converged to a final R = 0.028 and Rw = 0.029. [Re(py₃N)(CO)₃Cl] (C₁₈H₁₂ClN₄O₃Re) is triclinic, space group P1 with cell dimensions a = 13.761(2) Å, b = 14.636(6)Å, c = 11.110(2) Å, α = 110.70(2)°, β = 102.45(2)°, γ = 107.48(2)°, and Z = 4; full-matrix least-squares refinement on 3459 reflections with I ⩾ 2.5σ(I) converged to a final R = 0.038 and Rw = 0.039. If the synthetic procedure is undertaken under irradiation by visible light, for the ligand py₃N a species [Re(py₃N)(CO)₂Cl] (characterized by infrared spectroscopy and conductance measurements) is also formed, in which the ligand py₃N is tridentate. No analogous tridentate species is formed with the ligands tpy or py₃P, although there is evidence that it also forms for py₃CH.

Item ID: 22749
Item Type: Article (Research - C1)
ISSN: 1099-0739
Keywords: rhenium; carbonyl; terpyridyl; tris(2-pyridyl)amine; tris(2-pyridyl)methane; tris(2-pyridyl)phosphine; structure
Date Deposited: 10 Aug 2012 06:26
FoR Codes: 03 CHEMICAL SCIENCES > 0302 Inorganic Chemistry > 030207 Transition Metal Chemistry @ 100%
SEO Codes: 97 EXPANDING KNOWLEDGE > 970103 Expanding Knowledge in the Chemical Sciences @ 100%
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