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Complexes of Copper(I) Thiocyanate with Monodentate Phosphine and Pyridine Ligands and the P(,N) ‐Donor Diphenyl(2‐pyridyl)phosphine
Author(s) -
Bowmaker Graham A.,
Hanna John V.,
King Scott P.,
Marchetti Fabio,
Pettinari Claudio,
Pizzabiocca Adriano,
Skelton Brian W.,
Sobolev Alexandre N.,
Tăbăcaru Aurel,
White Allan H.
Publication year - 2014
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.201402791
Subject(s) - chemistry , denticity , thiocyanate , phosphine , pyridine , adduct , triphenylphosphine , medicinal chemistry , monoclinic crystal system , copper , stereochemistry , crystal structure , crystallography , inorganic chemistry , organic chemistry , catalysis
Copper(I) thiocyanate derivatives were prepared by the reaction of CuNCS with pyridine (py) and tertiary monophosphine ligands [PR 3 in general; in detail: PPh 3 , triphenylphosphine, P(4‐FPh) 3 , tris(4‐fluorophenyl)phosphine)], as well as the potentially bidentate ligand diphenyl(2‐pyridyl)phosphine (PPh 2 py). Mechanochemical methods were used in some cases to investigate stoichieometries that were not easily accessible by conventional solution syntheses. Three forms of the resulting adducts of CuNCS/PR 3 /py‐base (1:3– n : n ) stoichiometry―all containing four‐coordinate copper(I) atoms and monodentate N‐thiocyanate groups―were confirmed crystallographically. Mononuclear arrays are defined for [(PPh 2 py) 3– n (py) n Cu N CS], n = 0, 1, 2, the monodentate thiocyanate being N ‐coordinated in all; two polymorphs are observed for the n = 2 complex, both crystallizing in monoclinic P 2 1 ( Z = 2) cells with similar cell dimensions, but with aromatic components eclipsed about the Cu–P bond in the PPh 3 complex, and staggered in the PPh 2 py complex. Bridging thiocyanate groups are found in the 1:1:1 CuNCS/PPh 2 py/2‐methylpyridine (mpy) and P(4‐FPh) 3 /mpy complexes, wherein centrosymmetric dimers with eight‐membered central rings are obtained: [(R 3 P)(mpy)Cu( N C S ) 2 Cu(PR 3 )(mpy)], as is also the case in the parent 1:2 CuNCS/PPh 2 py adduct [(pyPh 2 P) 2 Cu( N C S ) 2 Cu(PPh 2 py) 2 ]. For the 1:1:1 Cu N C S /P(4‐FPh) 3 /py and PPh 3 /Brmpy (Brmpy = 3‐bromo‐4‐methylpyridine) adducts, and, likely, Cu N C S /PPh 2 py/py (1:1:1), single‐stranded polymers of the form [ ··· Cu( N C S )(PR 3 )(py‐base)(Cu) ··· ] (∞|∞) with linearly bridging NCS ligands were obtained. Some derivatives, representative of all forms, display medium to strong green to blue luminescence when excited with radiation at 365 nm. The 31 P CPMAS NMR spectroscopic data clearly differentiate the inequivalent phosphorus positions within each system, showing a wide range of 1 J ( 31 P, 63/65 Cu) values ranging from 965 Hz for [Cu( N CS)(PPh 2 py) 3 ] to 1540 Hz for dimeric [(4‐FPh) 3 P(mpy)Cu( N C S ) 2 Cu(P(4‐FPh) 3 )(mpy)], reflecting the large variations in the Cu–P bond length.