Evaluation of [C-12/C-11] Carbon Monoxide Binding to Copper(I) Tris(pyrazolyl) borate Complexes

TY - JOUR

T1 - Evaluation of [C-12/C-11] Carbon Monoxide Binding to Copper(I) Tris(pyrazolyl) borate Complexes

AU - Kealey, Steven

AU - White, Andrew J. P.

AU - Gee, Antony D.

AU - Long, Nicholas J.

PY - 2014/4

Y1 - 2014/4

N2 - The copper(I) coordination chemistry of tris(3-R-5-R-pyrazolyl)borate ligands (Tp(R,R)) bearing substituent groups attached to the pyrazole rings has been investigated under nitrogen and carbon monoxide atmospheres [1 (Tp(Ph,SMe)) R = Ph, R = SCH3; 2 (Tp(Py)) R = 2-pyridyl, R = H; 3 (Tp(Phos,Me)) R = 2-(diphenylphosphinyl)phenyl, R = CH3]. The reactivity is strongly dependent on the coordinating potential of the substituent groups; in the absence of CO, 1 formed an insoluble complex [Cu(Tp(Ph,SMe))](n) (1b), 2 formed a multinuclear species [Cu(Tp(Py))](n) (2a; tetrameric in solution, dimeric in the solid state) and 3 formed a discrete complex [Cu(Tp(Phos,Me))] (3a). Under a CO atmosphere, 1 displayed irreversible CO binding to form the complex [Cu(Tp(Ph,SMe))CO] (1c), 2 showed reversible CO binding between 2a and the mononuclear species [Cu(Tp(Py))CO] (2b), and 3 did not bind to CO, but instead formed 3a. The reactivity of the copper complexes of 1 and 2 with [C-11]carbon monoxide has been examined in the radiochemistry laboratory to investigate the reversibility of (CO)-C-11 binding. The solid-state structures of [Tl(Tp(Ph,SMe))] (1a), 1c and 2a were elucidated by X-ray crystallography.

AB - The copper(I) coordination chemistry of tris(3-R-5-R-pyrazolyl)borate ligands (Tp(R,R)) bearing substituent groups attached to the pyrazole rings has been investigated under nitrogen and carbon monoxide atmospheres [1 (Tp(Ph,SMe)) R = Ph, R = SCH3; 2 (Tp(Py)) R = 2-pyridyl, R = H; 3 (Tp(Phos,Me)) R = 2-(diphenylphosphinyl)phenyl, R = CH3]. The reactivity is strongly dependent on the coordinating potential of the substituent groups; in the absence of CO, 1 formed an insoluble complex [Cu(Tp(Ph,SMe))](n) (1b), 2 formed a multinuclear species [Cu(Tp(Py))](n) (2a; tetrameric in solution, dimeric in the solid state) and 3 formed a discrete complex [Cu(Tp(Phos,Me))] (3a). Under a CO atmosphere, 1 displayed irreversible CO binding to form the complex [Cu(Tp(Ph,SMe))CO] (1c), 2 showed reversible CO binding between 2a and the mononuclear species [Cu(Tp(Py))CO] (2b), and 3 did not bind to CO, but instead formed 3a. The reactivity of the copper complexes of 1 and 2 with [C-11]carbon monoxide has been examined in the radiochemistry laboratory to investigate the reversibility of (CO)-C-11 binding. The solid-state structures of [Tl(Tp(Ph,SMe))] (1a), 1c and 2a were elucidated by X-ray crystallography.

KW - Copper

KW - Carbonyl ligands

KW - Tridentate ligands

KW - Isotopic labelling

KW - POSITRON-EMISSION-TOMOGRAPHY

KW - IB METAL CHEMISTRY

KW - HYDROTRIS(PYRAZOLYL)BORATE LIGANDS

KW - TRIS(PYRAZOLYL)BORATE LIGAND

KW - NITROSYL COMPLEXES

KW - CO

KW - REACTIVITY

KW - PRESSURE

KW - SODIUM

KW - STATE

U2 - 10.1002/ejic.201301475

DO - 10.1002/ejic.201301475

M3 - Article

SN - 1434-1948

VL - 2014

SP - 1896

EP - 1905

JO - EUROPEAN JOURNAL OF INORGANIC CHEMISTRY

JF - EUROPEAN JOURNAL OF INORGANIC CHEMISTRY

IS - 11

ER -