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Phosphane Copper(I) Dicarboxylates: Synthesis and Their Potential Use as Precursors for the Spin‐coating Process in the Deposition of Copper
Author(s) -
Jakob Alexander,
Rüffer Tobias,
Ecorchard Petra,
Walfort Bernhard,
Körbitz Kathrin,
Frühauf Swantje,
Schulz Stefan E.,
Gessner Thomas,
Lang Heinrich
Publication year - 2010
Publication title -
zeitschrift für anorganische und allgemeine chemie
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.354
H-Index - 66
eISSN - 1521-3749
pISSN - 0044-2313
DOI - 10.1002/zaac.201000082
Subject(s) - chemistry , copper , crystallography , stereochemistry , medicinal chemistry , organic chemistry
Abstract Dicopper dicarboxylates [( R 3 P) m Cu X Cu(P R 3 ) m ] ( 5a , X = O 2 CCO 2 , R = Ph, m = 2; 5b , X = O 2 CCO 2 , R = n Bu, m = 3) were prepared by treatment of [Cu 2 O] ( 1a ) with HO 2 CCO 2 H ( 2a ) in presence of P R 3 ( 4a , R = Ph; 4b , R = n Bu). A further synthesis approach to mono‐ and dicopper dicarboxylates is given using an electrolysis cell equipped with Cu electrodes and charged with acids H 2 X and phosphanes R 3 P. Without addition of a base mononuclear [( n Bu 3 P) m Cu X H] ( 6a , m = 3, X H = O 2 CCO 2 H, 6b , m = 3, X H = O 2 CCH 2 CO 2 H, 6c , m = 3, X H = O 2 CCH 2 CH 2 CO 2 H, 6d , m = 2, X H = O 2 C‐2‐C 5 H 4 N‐6‐CO 2 H) was formed, whereas in presence of NEt 3 ( 3 ), the dicopper systems [( R 3 P) m Cu X Cu(P R 3 ) m ] ( 5a , X = O 2 CCO 2 , R = Ph, m = 2; 5b , X = O 2 CCO 2 , R = n Bu, m = 3; 5c , X = O 2 CCH 2 CO 2 , R = n Bu, m = 3; 5d , X = O 2 CCH 2 CH 2 CO 2 , R = n Bu, m = 3; 5e , X = O 2 C‐2‐C 5 H 4 N‐6‐CO 2 , R = n Bu, m = 3) were produced. When 6a reacted with [(tmeda)Zn( n Bu) 2 ] ( 7 ), trimetallic [(tmeda)Zn(( n Bu 3 P) 3 CuO 2 CCO 2 ) 2 ] ( 8 ) was accessible. In this heterobimetallic complex the Zn(tmeda) unit spans two CuO 2 CCO 2 entities. The molecular structures of 5a , 6a and 6d in the solid state were determined by single X‐ray structure analysis. Complexes 5a and 6a are monomers, whereas 6d creates in the solid state a linear open chain coordination polymer by hydrogen bridge formation. Characteristic for 6d is the somewhat distorted trigonal bipyrimidal arrangement around the copper atom with the n Bu 3 P ligands in axial and the C 5 H 3 NCO 2 H oxygen and nitrogen atoms in equatorial positions. In 5a the oxalate connectivity binds in a μ ‐1,2,3,4 fashion being part of a planar Cu 2 (oxalate) core. TG studies of several mono‐ and dicopper dicarboxylates were carried out. Release of the P R 3 ligands is recognized and the remaining Cu‐(di)carboxylate unit decomposes to afford elemental copper and CO 2 . The deposition of copper onto pieces of PVD‐Cu oxidized silicon wafers by applying the spin‐coating process and using 5c and 5d as precursors is discussed.