Au(2)-Au( l)-Au(4) 89.3(1) Au(4)-Au( I )-Se( 1) 76.0( 1) Au(4kA~(l)-P( 1) 105.7(2) Au(l)-Au(2)-Au(3) 91.0(1) Au(3)-Au(2)-Se(l) 84.5(1) A u ( ~) -A u ( ~) -P ( ~) 104.0(2) Au(~)-Au(~)-Au(~) 88.0(1) Au(4)-Au(3)-Se(2) 49.0( 1) Au(4)-Au(3)-P(3) 128.4(2) Au(3)-Au(4)-Se(2) 49.0(1) Au(l)-Se(ltAu(2) 80.3(1) Au(2)-Se( ltC(73) 100.8(8) Au(3)-Se(2kC(80) 102.1(9) Au(1)-P(1)-C(1) 111.4(6) C(1)-P(1)-C(7) 106.2(8) Au( 1)-Au(4)-Au(3) 90.2( 1) A u ( ~) -A u ( ~) -P ( ~) 129.9(2) C( 1 )-P( 1)-C( 13) 107.1(7) Au(2)-P(2)-C(19) 11 1.5(6) C( 19)-P(2)-C(25) 108.2(9) C( 19)-P(2)-C(3 1 ) 104.5(8) C(37)-P(3)-C(43) 105.8(9) C(37)-P(3) C(49) 105.6(8) Au(3)-P(3)-C(37) 11 1.1(7)

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Professor Joachim Strahle zum 60. Geburtstag gewidmel Inhaltsiibersicht. Bei der Umsetzung der Selenolato-Wolfram-Komplexe ~p ( c 0 )~W S e R ; R = CH2Ph, CH2SiMe3, mit den ungesattigten Komplexfragmenten M(CO)5(THF); M = Cr, W, bzw. den Komplexkationen Ph3PAu+ und ~p'(Co)~Fe+; cp' = CsH5, C5MeS, entstehen zweikernige Komplexe, in denen das Selenatom eine positive Ladung bzw. Partialladung tragt. Dabei konnten folgende Verbindungen charakterisiert werden: [~P ( C O )~W (~-S~C H~P~) C~( C O )~~ (I), [~P ( C~>~W (~-~~C H~P~) W ( C O ) S~ (4, [cp(C0)3W(p-p-C6H4(CH2secr(co)5]2)w(co)3cPl (3), [ C~( C O )~W (~-S~C H~P~) F~( C~)~C~] + C~O~-(4), [cp(CO)3W(p-SeCH2Ph)Fe(C0)2cp*]+C104-), (5) [C~(CO)~W(~-S~CH~P~)AUPP~~]+S~F~-(6), [ cp( C0)3W(p-SeCH2Ph)AuPPh31'ao, (7) und [ c~( C O )~W (~-S~C H~S~M~~) A U P P~~] + S~ (8). Die Strukturen der Verbindungen 1 , 2 , 4 und 8 konnten durch Einkristall-Rontgenstrukturanalyse aufgeklart werden (1: Raumgruppe P212121 (Nr. 19), Z = 16, a = 1744,5(3)pm, b = 2079,5(3) pm, c = 2435.7(5) pm; 2 Raumgruppe P1 (Nr. 2), Z = 8, a = 1318,94(14) pm, b = 1732,5(2) pm, c = 2119,9(2) pm, a = 8YL8O5(10)", p= 86,586(10)", y = 68,731(10)"; 4: Raumgruppe P1 (Nr.2), Z = 2 , a=828,0(5)pm, b=1027,4(5)pm, c = 1510,8(9) pm, a? 109,84(3)", p = 99,45(4)", y = 91,43(3)"; 8: Raumgruppe P1 (Nr. 2), Z = 4, a = 1325,7(2) pm, b = 1663,1(3) pm, c = 1925,2(3) pm, a= 95,869(14)", p= 103,091(12)", y = 112,871(10)"). Complexing Properties of Organometallic Selenolato Complexes. The Crystal Structures of [ cp( C0)3W(p-SeCH2Ph) W( CO),], [ cp( C 0)3 W (p-SeCH2P h) Cr ( C O),] , [ cp (CO), W (p-SeCH2P h)Fe (C O)2cp]+C104-, and [ cp( CO)3W (p-SeCH2SiMe3)AuPPh3]+SbFs-Abstract. The reaction of the selenolato tungsten complexes ~p ( c 0 )~W S e R ; R = CH2Ph, CH2SeSiMe3, with the unsaturated complexes M(C0)5(THF); M = Cr, W or the complex cations Ph3PAu' and ~p ' ( C o )~F e + ; cp' = C5H5, C5Me5, forms binuclear complexes, in which selenium possesses a formal 109.84(3)", /J' = 99.45(4)", y = 91,43(3)"; 8: space group P1 (Nr. 2), Z = 4, a = 1325.7(2) pm, b = 1663.1(3) pm, c = 1Y25.2(3) pm, a = 9.5.869(14)", j?= 103.091(12)", y = 112.871(10)").

Organotungsten-selenolato complexes were prepared in moganomonohalides. Moreover, the X-ray crystal structures derate yields by insertion of selenium into the alkali metal-of C6H5CH2W(C0)3cp (l), ~-[m-C6H4(CH2SeW(CO)~cp]2] tungsten bonds of MSeW(CO),cp (M = Li, Na) and subse-(3), ~L -[~-C , H~( C H~S~W ( C O )~C~}~](4), and C6H5CH[SeWquent reactions with the organohalides 0-, m-, and p-(CO)3cp]2 (5) were deJermined. In complex (l), the W-CH2 C6H4(CH2Br)2, C6H5CHBr2, m-C6H4(CHBr2)2 and C6H5CC1,. bond length is 2.374 A; the W-Se bond lengths in the com-The ??Se-NMR data of the new complexes are discussed and plexes 3, 4 , and 5 are all in the range 2.625-2.655 A, correcompared with those of related complexes derived from orsponding to W-Se single bonds.