Heteroleptic Copper(I) Complexes Prepared from Phenanthroline and Bis-Phosphine Ligands

被引:199
作者
Kaeser, Adrien [1 ,2 ,5 ]
Mohankumar, Meera [1 ,2 ]
Mohanraj, John [3 ]
Monti, Filippo [3 ]
Holler, Michel [1 ,2 ]
Cid, Juan-Jose [1 ,2 ]
Moudam, Omar [1 ,2 ,5 ]
Nierengarten, Iwona [1 ,2 ,4 ]
Karmazin-Brelot, Lydia [4 ]
Duhayon, Carine [5 ]
Delavaux-Nicot, Beatrice [5 ]
Armaroli, Nicola [3 ]
Nierengarten, Jean-Francois [1 ,2 ]
机构
[1] Univ Strasbourg, Lab Chim Mat Mol, F-67087 Strasbourg 2, France
[2] CNRS, UMR 7509, F-67087 Strasbourg 2, France
[3] CNR, Ist Sintesi Organ & Fotoreattivita, I-40129 Bologna, Italy
[4] Univ Strasbourg, Inst Chim, Serv Radiocristallog, F-67008 Strasbourg, France
[5] Univ Toulouse, INPT, CNRS, Lab Chim Coordinat,UPS,UPR 8241, F-31077 Toulouse 4, France
关键词
CRYSTAL-STRUCTURE; CU(I) COMPLEXES; ISOMERIZATION DYNAMICS; BRIDGING LIGANDS; EMISSIONS; SERIES; REACTIVITY; STATE; LUMINESCENCE; INTRALIGAND;
D O I
10.1021/ic4020042
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
Preparation of [Cu(NN)(PP)](+) derivatives has been systematically investigated starting from two libraries of phenanthroline (NN) derivatives and bis-phosphine (PP) ligands, namely, (A) 1,10-phenanthroline (phen), neocuproine (2,9-dimethyl-1,10-phenanthroline, dmp), bathophenanthroline (4,7-diphenyl-1,10-phenanthroline, Bphen), 2,9-diphenethyl-1,10-phenanthroline (dpep), and 2,9-diphenyl-1,10-phenanthroline (dpp); (B) bis(diphenylphosphino)methane (dppm), 1,2-bis(diphenylphosphino)ethane (dppe), 1,3-bis(diphenylphosphino)propane (dppp), 1,2-bis(diphenylphosphino)benzene (dppb), 1,1'-bis(diphenylphosphino)ferrocene (dppFc), and bis[(2-diphenylphosphino)phenyl] ether (POP). Whatever the bis-phosphine ligand, stable heteroleptic [Cu(NN)(PP)](+) complexes are obtained from the 2,9-unsubstituted-1,10-phenanthroline ligands (phen and Bphen). By contrast, heteroleptic complexes obtained from dmp and dpep are stable in the solid state, but a dynamic ligand exchange reaction is systematically observed in solution, and the homoleptic/heteroleptic ratio is highly dependent on the bis-phosphine ligand. Detailed analysis revealed that the dynamic equilibrium resulting from ligand exchange reactions is mainly influenced by the relative thermodynamic stability of the different possible complexes. Finally, in the case of dpp, only homoleptic complexes were obtained whatever the bis-phosphine ligand. Obviously, steric effects resulting from the presence of the bulky phenyl rings on the dpp ligand destabilize the heteroleptic [Cu(NN)(PP)](+) complexes. In addition to the remarkable thermodynamic stability of [Cu(dpp)(2)]BF4, this negative steric effect drives the dynamic complexation scenario toward almost exclusive formation of homoleptic [Cu(NN)(2)](+) and [Cu(PP)(2)](+) complexes. This work provides the definitive rationalization of the stability of [Cu(NN)(PP)](+) complexes, marking the way for future developments in this field.
引用
收藏
页码:12140 / 12151
页数:12
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