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Synthesis of the Germanium(I) Compounds [Ge 2 Hal 4 ] 2– and Their Reductive Condensation to Octahedral [Ge 6 ] 2– Clusters in an Organometallic Environment
Author(s) -
Renner Gerd,
Kircher Peter,
Huttner Gottfried,
Rutsch Peter,
Heinze Katja
Publication year - 2000
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/(sici)1099-0682(200005)2000:5<879::aid-ejic879>3.0.co;2-s
Subject(s) - chemistry , germanium , octahedron , halide , metathesis , reductive elimination , cluster (spacecraft) , condensation , organometallic chemistry , yield (engineering) , oxidation state , condensation reaction , crystallography , medicinal chemistry , inorganic chemistry , crystal structure , organic chemistry , catalysis , physics , materials science , silicon , computer science , programming language , metallurgy , polymerization , thermodynamics , polymer
GeI 2 reacts with [M 2 (CO) 10 ] 2– (M = Cr, W) leading to reductive coupling of two GeI 2 units to produce the [Ge 2 I 4 ] 2– ligands of [{(OC) 5 M}I 2 Ge–GeI 2 {M(CO) 5 }] 2– ( 1a and 2a ). The [Ph 4 P] salts of these anions have been characterised by X‐ray structure analyses as have the [Ph 4 P] salts of [{(OC) 5 M}Cl 2 Ge–GeCl 2 {M(CO) 5 }] 2– ( 1b and 2b ) obtained from the iodo derivatives 1a and 2a by halide metathesis with [Ph 4 P]Cl. Treatment of GeI 2 with [W 2 (CO) 10 ] 2– in the presence of 2,2′‐bipyridine leads to [{(OC) 5 W}I 2 Ge–Ge(bipy){W(CO) 5 }] ( 3 ). The digermanium ligands in 1 – 3 contain germanium in the unconventional formal oxidation state +I. Reductive condensation of [{(OC) 5 Cr}I 2 Ge–GeI 2 {Cr(CO) 5 }] 2– ( 1a ) by addition of [Cr 2 (CO) 10 ] 2– leads to the octahedral cluster [{(OC) 5 Cr} 6 Ge 6 ] 2– ( 4 ) in a yield of 40%. The sequence of reactions as reported describes the first systematic approach to the synthesis of [E 6 ] 2– clusters.