TY - JOUR

T1 - Low-Nuclearity Alkynyl d10 Clusters Supported by Chelating Multidentate Phosphines

AU - Belyaev, Andrey

AU - Dau, Thuy Minh

AU - Jänis, Janne

AU - Grachova, Elena V.

AU - Tunik, Sergey P.

AU - Koshevoy, Igor O.

N1 - Funding Information: Financial support from the Academy of Finland (grant 268993, I.O.K., synthesis and XRD study) and the Russian Science Foundation (grant 16-13-10064, E.V.G., spectroscopic characterization in solution and photophysical measurements) Publisher Copyright: © 2016 American Chemical Society. Copyright: Copyright 2017 Elsevier B.V., All rights reserved.

PY - 2016/11/14

Y1 - 2016/11/14

N2 - The coordination chemistry of the tri- and tetradentate chelating phosphines (2-PPh2C6H4)2P(O)Ph (P3O) and (2-PPh2C6H4)3P (P4) with respect to d10 copper subgroup metal ions has been investigated. Depolymerization of (MC2R)n (M = Cu, Ag) with P4 affords the series of mono- and trinuclear complexes (P4)CuC2Ph (1), (P4)Cu3(C2Ph)3 (2), (P4)Ag3(C2Ph) (Hal)2 (Hal = Cl (3), Br (4), I (5)). Reactions of the M+ (M = Cu, Ag) ions with (M′C2R)n (M′ = Cu, Ag, Au) acetylides in the presence of P4 yield the family of dinuclear species [(P4)MM′(C2R)]+ (6-12), which comprise the Cu2/Ag2 (6, 7; R = Ph), AuCu (8-10; R = Ph, C(OH)Me2, C(OH)Ph2), and AuAg (11, 12; R = Ph, C(OH)Ph2) metal cores. A related triphosphine, (2-PPh2C6H4)2PPh (P3), applied in a similar protocol undergoes partial oxidation and leads to the heterotrimetallic clusters [{(P3O)M}2Au(C2R)2]+ (M = Cu, R = C(OH)Ph2, 13; M = Ag, R = C(OH)Ph2, 14; M = Ag, R = Ph, 15), which can be prepared more efficiently starting from the oxidized ligand P3O. The structures of the complexes 1-4 and 6-15 were established by single-crystal X-ray crystallography. According to the variable-temperature 1H and 31P{1H} NMR experiments, compounds 1-12 demonstrate fluxional behavior in solution. The title complexes do not show appreciable luminescence in solution at 298 K, and the photophysical properties of 1-15 were studied in the solid state. The observed phosphorescence (em up to 0.46, λem from 440 to 635 nm) is assigned to cluster-centered transitions mixed with some MLCT d →π∗(alkynyl) character.

AB - The coordination chemistry of the tri- and tetradentate chelating phosphines (2-PPh2C6H4)2P(O)Ph (P3O) and (2-PPh2C6H4)3P (P4) with respect to d10 copper subgroup metal ions has been investigated. Depolymerization of (MC2R)n (M = Cu, Ag) with P4 affords the series of mono- and trinuclear complexes (P4)CuC2Ph (1), (P4)Cu3(C2Ph)3 (2), (P4)Ag3(C2Ph) (Hal)2 (Hal = Cl (3), Br (4), I (5)). Reactions of the M+ (M = Cu, Ag) ions with (M′C2R)n (M′ = Cu, Ag, Au) acetylides in the presence of P4 yield the family of dinuclear species [(P4)MM′(C2R)]+ (6-12), which comprise the Cu2/Ag2 (6, 7; R = Ph), AuCu (8-10; R = Ph, C(OH)Me2, C(OH)Ph2), and AuAg (11, 12; R = Ph, C(OH)Ph2) metal cores. A related triphosphine, (2-PPh2C6H4)2PPh (P3), applied in a similar protocol undergoes partial oxidation and leads to the heterotrimetallic clusters [{(P3O)M}2Au(C2R)2]+ (M = Cu, R = C(OH)Ph2, 13; M = Ag, R = C(OH)Ph2, 14; M = Ag, R = Ph, 15), which can be prepared more efficiently starting from the oxidized ligand P3O. The structures of the complexes 1-4 and 6-15 were established by single-crystal X-ray crystallography. According to the variable-temperature 1H and 31P{1H} NMR experiments, compounds 1-12 demonstrate fluxional behavior in solution. The title complexes do not show appreciable luminescence in solution at 298 K, and the photophysical properties of 1-15 were studied in the solid state. The observed phosphorescence (em up to 0.46, λem from 440 to 635 nm) is assigned to cluster-centered transitions mixed with some MLCT d →π∗(alkynyl) character.

UR - http://www.scopus.com/inward/record.url?scp=84995528746&partnerID=8YFLogxK

U2 - 10.1021/acs.organomet.6b00701

DO - 10.1021/acs.organomet.6b00701

M3 - Article

VL - 35

SP - 3763

EP - 3774

JO - Organometallics

JF - Organometallics

SN - 0276-7333

IS - 21

ER -