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- Title
Systematic Synthesis of Di-, Tri-, and Tetranuclear Homo- and Heterometal Complexes Using a Mononuclear Copper Synthon with a Tetradentate Amino Alcohol Ligand.
- Authors
Nakajima, Takayuki; Yamashiro, Chisako; Taya, Megumi; Kure, Bunsho; Tanase, Tomoaki
- Abstract
The reaction of Cu(NO3)2 ·3H2O with an N2O2 tetradentate amino alcohol, N, N-dibenzyl- N′, N′-bis(2-hydroxyethyl)ethylenediamine (H2L), afforded the mononuclear copper complex [Cu(H2L)(NO3)](NO3) ( 1), which has been used to construct a series of di-, tri-, and tetranuclear homo- and heterometallic complexes. Complex 1 dimerized in the presence of NEt3 to form the Cu2 complex [Cu2(HL)2](NO3)2 ( 2) by the deprotonation of one of the two hydroxy groups in the H2L ligand. The reaction of 1 with Cu(OCOH)2 in the presence of NEt3 afforded the Cu3 complex [Cu3(HL)2(OCOH)2](NO3)2 ( 5). The metalloligand {Cu(HL)}+ derived from 1 reacted with M(OAc)2 (M = Cu, Co, Zn, Ni) in the absence of NEt3 to form the asymmetric CuM dinuclear complexes [CuM(HL)(OAc)(NO3)2] [M = Cu ( 3a), Co ( 3b), Zn ( 3c), Ni ( 3d)], whereas in the presence of NEt3 a unit of M(OAc) was captured by two metalloligands to give the bent CuMCu trinuclear complexes [Cu2M(HL)2(OAc)2(NO3)](NO3) [M = Cu ( 4a), Co ( 4b), Mn ( 4c)], which were further transformed into the linear CuMCu trinuclear complexes [Cu3(HL)2{(PhO)2PO2}2](NO3)2 ( 7a) and [Cu2M(HL)2{(PhO)2PO2}2(MeOH)2](NO3)2 [M = Co ( 7b), Mn ( 7c)] with the aid of diphenyl phosphate bridging ligands. When (PhO)PO2(OH) was used as an auxiliary bridging ligand in the reaction of 1 with M(OAc)2 and NEt3, the Cu2M2 tetranuclear complexes [Cu2M2(HL)2{(PhO)PO3}2(NO3)2] [M = Co ( 8a), Zn ( 8b)] were synthesized. These results demonstrate that the mononuclear copper synthon with the N2O2 tetradentate amino alcohol ligand {Cu(H2L)}2+ generates the quite useful metalloligand {Cu(HL)}+ by the deprotonation of a hydroxy group, and subsequent reactions lead to the construction of a series of homo- and heterometal complexes containing Cu2, CuM (M = Cu, Co, Zn, Ni), bent-CuMCu (M = Cu, Co, Mn), linear-CuMCu (M = Cu, Co, Mn), and Cu2M2 (M = Co, Mn) cores in a systematic and selective manner.
- Subjects
LIGANDS (Chemistry); METAL compounds synthesis; TRANSITION metal complexes; METAL complexes; AMINO alcohols; CHEMICAL synthesis
- Publication
European Journal of Inorganic Chemistry, 2016, Vol 2016, Issue 17, p2764
- ISSN
1434-1948
- Publication type
Article
- DOI
10.1002/ejic.201600142