Premium
Tri‐ n ‐Butyl‐Phosphan‐Silber(I)‐Komplexe mit Carboxylat‐, Troponolat‐ bzw. N‐Hydroxyphthalimid‐Teilstrukturen; Synthese und Verwendung als Spin‐On‐Precursoren
Author(s) -
Jakob A.,
Schmidt H.,
Walfort B.,
Rheinwald G.,
Frühauf S.,
Schulz S.,
Gessner T.,
Lang H.
Publication year - 2005
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.200400510
Subject(s) - chemistry , oxalate , carboxylate , yield (engineering) , oxalic acid , medicinal chemistry , phthalimide , stereochemistry , inorganic chemistry , physics , organic chemistry , thermodynamics
Tri‐ n ‐Butyl‐Phosphane Silver(I) Complexes with Carboxylate‐, Tropolonate‐ or N‐Hydroxyphthalimide Building Blocks; Synthesis and their Use as Spin‐on Precursors Treatment of AgNO 3 ( 1 ) with one equivalent of HX ( 2a , X = trop; 2b , X = phthal; trop = troponolate; phthal = N‐hydroxy‐phthalimide anion) in presence of NEt 3 affords the silver(I) salts [AgX] ( 3a , X = trop; 3b , X = phthal) in quantitative yield. When instead of 2a and 2b oxalic acid ( 4a ) or quadratic acid (1,2‐dihydroxycyclobutene‐3,4‐dione) ( 4b ) are reacted with 1 under similar reaction conditions, then the corresponding disilver salts [Ag 2 E] ( 5a , E = ox; 5b , E = quad; ox = oxalate; quad = quadratic acid dianion) are accessible in excellent yield. The reaction of 3 and 5 with m equivalents of n Bu 3 P ( 6 ) produces the phosphane silver(I) complexes ( n Bu 3 P) m AgX (m = 1: 7a , X = trop; 7b , X = phthal; m = 2: 8a , X = trop; 8b , X = phthal) and ( n Bu 3 P) m Ag‐E‐Ag(P n Bu 3 ) m (m = 1: 9a , E = ox; 9b , E = quad; m = 2: 10a , E = ox; 10b , E = quad; m = 3: 11a , E = ox; 11b , E = quad), which can be isolated after appropriate work‐up as colourless ( 9 – 11 ), yellow ( 7a , 8a ) or red‐purple ( 7b , 8b ) species. The solid‐state structures of 7b and 9a are reported. Complex 7b exists of two ( n Bu 3 P)Ag(phthal) units in which the oxygen atoms of the N‐hydroxyphthalimide anions are μ‐bridging both silver atoms. The thus formed 4‐membered Ag 2 O 2 cycle is planar and the silver atoms show the coordination number 3. Complex 9a exhibits a planar dinuclear structure with the anticipated oxalate building block in a μ‐1,2,3,4 bridging mode. As typical for 7b also for 9a a tricoordinated silver(I) ion is present, whereby the phosphanes act as neutral capping ligands. The thermal behaviour of selected species ( 7b , 8b , 9a , 10a , 11a and 11b ) was studied by applying thermogravimetry. The decomposition of the latter complexes starts between 100–160 °C and is completed in the region of 350–400 °C. One – four decomposition steps are typical. The decomposition of 9a was studied in detail. Elimination of n Bu 3 P occurs at first, while loss of CO 2 from in‐situ generated [Ag 2 ox] gives elemental silver. For that reason, 9a was used as spin‐on precursor in the deposition of silver on TiN‐coated oxidized silicon wafers. REM studies showed that closed and homogeneous silver layers were formed. The resistivity was determined to 3.4 μΩcm.