Direkter Metallaustausch an Germylidin‐Tricobalt‐Clustern

Abstract

Es wurden die Reaktionen der Cluster RGeCo3(CO)9 (1, R  Me, Ph, tBu) und ihrer Folgeprodukte mit den Metallaustausch‐Reagenzien [CpMo(CO)3]2, [CpW(CO)3]2, [CpNiCO]2 und Na2Fe(CO)4 untersucht. Aus 1 und [CpM(CO)3]2 (M  Mo, W) entstanden die Cluster RGeCo2MCp(CO)8 (4, 5), mit [CpNiCO]2 traten Umlagerungsreaktionen ein, und Na2Fe(CO)4 führte nur für R  tBu zu tBuGeCo2Fe(CO)9H (6). Von den Clustern tBuGeCo2MCp(CO)8 (4c, 5c) führte erneuter Metallaustausch zu den entsprechenden Hetero‐Clustern mit CoMo2‐,CoMoW‐, CoMoNi‐ und CoMoFe‐Gerüst. Bei den Clustern LnM  GeCo3(CO)9 (11) mit LnM  Cp(CO)3Mo, Cp(CO)3W, Cp(CO)2Fe, (CO)2Fe, Co und CpCONi trat mit [CpMo(CO)3]2 ein Austausch entweder der externen Organometall‐Einheit oder der im Cluster befindlichen Co(CO)3‐ Einheit ein. Als neue Verbindungen entstanden dabei LnM  GeCo2MoCp(CO)8 (12) mit LnM  Cp(CO)3Mo, Cp(CO)3W und Cp(CO)2Fe. Von tBuGeCoMoFeCp(CO)8H (10) und Cp(CO)3W  GeCo2MoCp(CO)8 (12b) wurden Kristallstrukturanalysen durchgeführt.

Mixed-Chalcogenide, Mixed-Metal Carbonyl Clusters. Synthesis and Characterization of Cp2Mo2Fe2(μ4-Te)(μ3-E)(μ3-E‘)(CO)6 (E, E‘ = Te; E = S, E‘ = Te; E, E‘ = S; E = S, E‘ = Se), Cp2Mo2Fe2(μ3-Te)(μ3-E)(CO)7, and Cp2Mo2Fe(μ3-E)(CO)7 (E = S, Te)

“…It is comparable with the Mo−Mo bond distance of 3.096(1) Å in the Se compound Cp 2 Mo 2 Fe(μ 3 -Se)(CO) 7 12 and the average Mo−Mo bond distance of 3.116 Å in Cp 3 Mo 3 (CO) 6 (μ 3 -As) . The average Fe−Mo bond distance of 2.812 Å in 4 is shorter than the Fe−Mo bond distances of 2.905 Å in H(Cp)MoCoFe(CO) 8 (μ 3 -GeBu t ), 2.95 Å in (MeCp) 2 Mo 2 Fe 2 S 4 (CO) 6 , and 2.9357 Å in 1 but similar to the average Fe−Mo bond distances of 2.835 Å in Cp 2 Mo 2 Fe(μ 3 -Se)(CO) 7 and 2.847 Å in Cp 2 Mo 2 Fe 2 (μ 4 -Se)(μ 3 -Se) 2 (CO) 6 . All other bond metricals of 4 are unexceptional.…”

Triple Bonding to Germanium: Characterization of the Transition Metal Germylynes (η5-C5H5)(CO)2M⋮Ge-C6H3-2,6-Mes2(M = Mo, W; Mes = −C6H2-2,4,6-Me3) and (η5-C5H5)(CO)2M⋮Ge-C6H3-2,6-Trip2(M = Cr, Mo, W; Trip = −C6H2-2,4,6-i-Pr3) and the Related Single Bonded Metallogermylenes (η5-

“…Several complexes featuring W−Ge single bonds have been characterized. These include the species η 5 -C 5 H 5 (CO) 3 WGeCo 2 (CO) 3 Mo(η 5 -C 5 H 5 )(CO) 2 (W−Ge = 2.589(4) Å), (η 5 -C 5 H 5 ) 2 W(H)(μ 2 -GeMe 2 )(μ-GeMe)(μ−η 5 -C 5 H 4 )W(η 5 -C 5 H 5 ) (W−Ge = 2.605(2) Å), W 2 (GePh 3 ) 2 (NMe 2 ) 4 (W−Ge = 2.625(1) Å), and (η 5 -C 5 H 5 ) 2 W(SiMe 3 )Ge(Me 2 Cl) (W−Ge = 2.542(1) Å), which have W−Ge single bonds, and the formally double-bonded germylene (germanediyl) complexes, (CO) 5 WGe(Cl)(η 2 -C 5 Me 5 ) (W−Ge = 2.571(1) Å), (CO) 5 WGe(η 2 -C 5 H 5 ){CH(SiMe 3 ) 2 } (W−Ge = 2.632(4) Å), (OC) 5 WGe(SeMes*) 2 (W−Ge = 2.528(1) Å, Mes* = C 6 H 2 -2,4,6- t -Bu 3 ), (CO) 5 WGe(Tbt)Trip (W−Ge = 2.5934(8) Å, Trip = −C 6 H 2 -2,4,6- i -Pr 3 , Tbt = C 6 H 2 -2,4,6-{CH(SiMe 3 ) 2 } 3 ). In addition, there is the ion [W(CO) 5 (GeH 3 )] - which was reported to have an unusually short W−Ge distance of 2.39 Å.…”

Contents

“…In a green compound with an FeGeMoCo cluster [343] The structure of the reddish-black cp(CO) 2 FeSnClCo(CO) 4 Ni(CO)cp [344] is shown in Fig. 19.…”

“…The shortest bonds to iron in the case of a non-transition metal is found for Fe-Ge, which is 2.321(10) A. [343] The respective bond length for the transition metals is for Fe-Co: 2.422(1) A. [335] The only compound displaying isomerism is (CO) 3 Fe^3-HC=CMe)RhcpCo 2 (CO) 5 , where the compound crystallizes in both orthorhombic and monoclinic crystal systems.…”