The reaction of white phosphorus with the coordinatively unsaturated [M(CO) 3 (PR 3 ) 2 ] complexes (M ) Mo, W; R ) Cy, Pr i ) yields the compounds [M(CO) 3 -(PR 3 ) 2 (η 1 -P 4 )] in which the P 4 -tetrahedron is end-on bonded to the metal. In the same manner reacts Ar′CtP (Ar′ ) C 6 H 2 Bu t 3 -2,4,6) with this complex to give [W(CO) 3 -(PCy 3 ) 2 (η 1 -PtCAr′)]. The X-ray structures of the products are discussed, and for the P 4 -unit in [W(CO) 3 (PCy 3 ) 2 (η 1 -P 4 )] the librational analysis was performed to correct their translational and rotational motions.
The reaction of [{Cp(CO) 2 Fe}BiCl 2 ] (1a) with [Co(CO) 4 ]leads to the formation of the first heteroleptic substituted bismuthane, [(µ 3 -Bi){Co(CO) 4 } 2 {Fe(CO) 2 Cp}] (2). When the "open" complex 2 is irradiated, the heterocubane [Bi 4 {Co(CO) 3 } 4 ] (3) is formed. [{Cp′′(CO) 2 Fe}BiCl 2 ] (1b; Cp′′ ) η 5 -C 5 H 3 -tBu 2 ) reacts with [Fe(CO) 4 ] 2to give the nido cluster [{Fe 3 (CO) 9 }{µ-BiFe(CO) 2 Cp′′} 2 ] (4) and to give the complex [Bi 4 {µ 3 -Fe(CO) 3 } 3 {Fe(CO) 2 Cp′′} 2 ] (5); the latter contains a distorted-tetrahedral Bi 4 cluster core in which three of the faces are capped by Fe(CO) 3 moieties. The reaction of 1b with Na 2 [W 2 (CO) 10 ] yields the Bi-bridged tetrahedral W 2 Bi 2 cluster [{W 2 (CO) 8 }(µ,η 2 -Bi 2 ){µ-BiFe(CO) 2 Cp′′}] (6). In contrast to this, the molybdenumsubstituted analogue [{Cp′′(CO) 3 Mo}BiCl 2 ] (7) reacts with Na 2 [Fe(CO) 4 ] to yield the arachno cluster [{Fe 2 (CO) 6 }{Fe(CO) 4 }{µ 3 -BiMo(CO) 3 Cp′′} 2 ] (9). When 7 is reacted with Na 2 [W(CO) 5 ], the complex [{Cp′′(CO) 3 Mo} 2 BiCl] (10) is obtained. The decomposition of compound 7 in THF leads to the ionic complex [(Cp′′MoCO) 2 (µ-Cl) 3 ] 2 [Bi 2 Cl 8 (thf) 2 ] (8). The crystal structures of all products are presented.
Die Reaktion von [CpW(CO)3]– mit PCl3 führt zu den Dichlorphosphan‐Komplexen [{Cp(CO)3W}PCl2] (1) und [{Cp(CO)3W}PCl2{WCl(CO)2Cp}] (2). Die Kristallstruktur von 2 belegt den Charakter eines Lewis‐Säure/Base Adduktes dieser Verbindung. Die Reaktion von 1 bzw. von [Cr(CO)5Cp*PCl2] mit Metallaten des Typs [M(CO)3Cp′]– (M = Mo, W; Cp′ = η5‐C5H4tBu) ergibt die cyclo‐P3‐Ligandkomplexe [(η3‐P3)MCp′(CO)3] (3) (M = W) und (4) (M = Mo) bzw. [(μ,η2‐P2{Cr(CO)5}2){Mo(CO)2Cp}2] (5) und [(μ3‐PW(CO)3Cp′){W(CO)2Cp′}2] (6). Komplex 6 weist ein planares, homoleptisches W3P‐Gerüst auf, welches innerhalb des W2P‐Dreirings delokalisierte Mehrfachbindungen aufweist. Ferner führt die Reduktion von [(CO)5WPCl3] mit Magnesium zur Bildung des Phosphinidenkomplexes [{(CO)5W}2PCl], wohingegen bei der Reduktion von [Cp(CO)3WPCl2] (1) mit Mg neben P4‐Phosphor der cyclo‐P3‐Komplex 3 entsteht.
The reaction of [{Cpx(CO)2Fe}SbCl2] [1a: Cpx = η5‐C5H3tBu2‐1,3 (Cp"); 1b: Cpx = η5‐C5Me5 (Cp*)] with Na2[Fe(CO)4] or K[Co(CO)4] affords the novel antimony‐transition metal cluster compounds [{μ3‐SbFe(CO)2Cp"}3{Fe(CO)3}4] (2), [{Fe3(CO)9}{μ3‐SbFe(CO)2Cp"}2] (3) and [{μ4‐SbFe(CO)2Cp*}2{Co4(CO)10(μ‐CO)}] (4). All products were characterised by X‐ray structure analyses and other methods. Cluster 2 reveals a novel Sb3Fe4 core, which does not follow the Wade−Mingos rules. Cluster 3 forms a square‐pyramidal nido‐cluster. The Sb2Co4 cluster core of 4 derives from a pentagonal bipyramid and consists of apical Sb and equatorial Co atoms with one missing pentagonal core atom.
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