Complexes of Copper(I) Thiocyanate with Monodentate Phosphine and Pyridine Ligands and the P(, N)‐Donor Diphenyl(2‐pyridyl)phosphine. Issue 35 (6th November 2014)

• Record Type: Journal Article
• Authors: 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.
• Is Part Of: European journal of inorganic chemistry. Issue 35(2014)
• Page Start: 6104
• Page End: 6116
• Publication Date: 2014-11-06
• Subjects: Copper -- N, P ligands -- Coordination modes -- Structure elucidation; Chemistry, Inorganic -- Periodicals; Organometallic chemistry -- Periodicals; Bioinorganic chemistry -- Periodicals; Solid state chemistry -- Periodicals; 546
• DOI: 10.1002/ejic.201402791
• Languages: English
• ISSNs: 1434-1948

Abstract

Abstract: Copper(I) thiocyanate derivatives were prepared by the reaction of CuNCS with pyridine (py) and tertiary monophosphine ligands [PR3 in general; in detail: PPh3, triphenylphosphine, P(4‐FPh)3, tris(4‐fluorophenyl)phosphine)], as well as the potentially bidentate ligand diphenyl(2‐pyridyl)phosphine (PPh2 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/PR3 /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 [(PPh2 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 21 ( Z = 2) cells with similar cell dimensions, but with aromatic components eclipsed about the Cu–P bond in the PPh3 complex, and staggered in the PPh2 py complex. Bridging thiocyanate groups are found in the 1:1:1 CuNCS/PPh2 py/2‐methylpyridine (mpy) and P(4‐FPh)3 /mpy complexes, wherein centrosymmetric dimers with eight‐membered central rings are obtained: [(R3 P)(mpy)Cu( N C S )2 Cu(PR3 )(mpy)], as is also the case in the parent 1:2 CuNCS/PPh2 py adduct [(pyPh2 P)2 Cu( N C S )2 Cu(PPh2 py)2 ]. For the 1:1:1 Cu N C S /P(4‐FPh)3 /py and PPh3 /Brmpy (Brmpy = 3‐bromo‐4‐methylpyridine) adducts, and, likely, Cu N C S /PPh2 py/py (1:1:1), single‐stranded polymers of the form [··· Cu( N C S )(PR3 )(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)(PPh2 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. Abstract : Mononuclear [(PR3 ) x CuSCN(py)2 ], dinuclear [{(PR3 )CuSCN(py)}2 ], and single‐stranded polymers of the form [··· Cu(PR3 )(py‐base)(SCN)Cu··· ] were synthesized and have been characterized by IR spectroscopy, single‐crystal X‐ray diffraction and 31 P CPMAS NMR spectroscopic studies.