%0 Journal Article %1 Sieger.2005 %A Sieger, Monika %A Vogler, Conny %A Klein, Axel %A Knoedler, Axel %A Wanner, Matthias %A Fiedler, Jan %A Zalis, Stanislav %A Snoeck, Theo L. %A Kaim, Wolfgang. %D 2005 %J Inorganic Chemistry %K arsine bipyrimidine complex complex;electrochem complex;luminescence copper dinuclear phosphine prepn redn structure structure;crystal %N 13 %P 4637--4643 %R 10.1021/ic050207z %T Geometrical and Electronic Structures of Dinuclear Complex Ions (μ-bpym)Cu(EAr3)222+ with Intramolecular \dqOrganic Sandwich\dq Formation (E = P or As; Ar = Aryl; bpym = 2,2'-Bipyrimidine) %V 44 %X (μ-Bpym)Cu(AsPh3)22(BF4)2 (1) was prepd. and studied in comparison with the triphenylphosphine analog (2). Qual., the structure of 1 with characteristically distorted copper(I) coordination caused by Ph/bpym/Ph sandwich interactions is similar to that of 2 and is approx. reproduced by DFT calcns. for the model complex ions (μ-bpym)Cu(EMe2Ph)222+, E = P or As. In contrast, the dinuclear (μ-bpym)Cu(P(3-Me-C6H4)3)22(BF4)2 (3) displays a distinctly less distorted metal coordination geometry due to the steric requirements of the Me groups in the meta-tolyl substituents. The electrochem. redn. of 1 is less reversible than for the phosphine analogs; the 1-electron-reduced form 1.bul.- exhibits a broad, unresolved EPR signal at g = 2.0023. Resonance Raman spectroscopy of 1 shows the typical vibrations of the bpym ligand in agreement with the MLCT assignment of the long-wavelength transitions \textless500 nm. All three dinuclear complexes exhibit luminescence at room temp. in the solid and in soln. on SciFinder(R)

@article{Sieger.2005, abstract = {{(μ-Bpym)[Cu(AsPh3)2]2}(BF4)2 (1) was prepd. and studied in comparison with the triphenylphosphine analog (2). Qual., the structure of 1 with characteristically distorted copper(I) coordination caused by Ph/bpym/Ph sandwich interactions is similar to that of 2 and is approx. reproduced by DFT calcns. for the model complex ions {(μ-bpym)[Cu(EMe2Ph)2]2}2+, E = P or As. In contrast, the dinuclear {(μ-bpym)[Cu(P(3-Me-C6H4)3)2]2}(BF4)2 (3) displays a distinctly less distorted metal coordination geometry due to the steric requirements of the Me groups in the meta-tolyl substituents. The electrochem. redn. of 1 is less reversible than for the phosphine analogs; the 1-electron-reduced form 1.bul.- exhibits a broad, unresolved EPR signal at g = 2.0023. Resonance Raman spectroscopy of 1 shows the typical vibrations of the bpym ligand in agreement with the MLCT assignment of the long-wavelength transitions {\textless}500 nm. All three dinuclear complexes exhibit luminescence at room temp. in the solid and in soln. [on SciFinder(R)]}, added-at = {2022-06-15T11:26:56.000+0200}, author = {Sieger, Monika and Vogler, Conny and Klein, Axel and Knoedler, Axel and Wanner, Matthias and Fiedler, Jan and Zalis, Stanislav and Snoeck, Theo L. and Kaim, Wolfgang.}, biburl = {https://puma.ub.uni-stuttgart.de/bibtex/24a26a4e6889235b96ba3e4c4164ba828/huebleriac}, doi = {10.1021/ic050207z}, interhash = {695628b0ba4240e1e3d6fbf522cebc8d}, intrahash = {4a26a4e6889235b96ba3e4c4164ba828}, issn = {0020-1669}, journal = {Inorganic Chemistry}, keywords = {arsine bipyrimidine complex complex;electrochem complex;luminescence copper dinuclear phosphine prepn redn structure structure;crystal}, number = 13, pages = {4637--4643}, timestamp = {2022-06-15T09:26:56.000+0200}, title = {Geometrical and Electronic Structures of Dinuclear Complex Ions {(μ-bpym)[Cu(EAr3)2]2}2+ with Intramolecular {\dq}Organic Sandwich{\dq} Formation (E = P or As; Ar = Aryl; bpym = 2,2'-Bipyrimidine)}, volume = 44, year = 2005 }