1. Chemistry of Triple‐Decker Sandwich Complexes Containing Four‐Membered Open B2E2 Rings (E = S or Se).
- Author
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Joseph, Benson, Barik, Subrat Kumar, Ramalakshmi, Rongala, Kundu, Gargi, Roisnel, Thierry, Dorcet, Vincent, and Ghosh, Sundargopal
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COMPLEX compounds ,BORANES ,CHEMICAL reactions ,THERMOLYSIS ,CHALCOGENS - Abstract
Building upon our earlier studies of cobaltaheteroboranes, we explore the chemistry with heavier group 9 metals. Reaction of [Cp*M(µ‐Cl)Cl
x ]2 (Cp* = η5 ‐C5 Me5 ; M = Co, x = 0; M = Rh or Ir, x = 1) with [LiBH4 ·THF], followed by thermolysis with an excess of chalcogen powders (S or Se), affords dimetallaheteroboranes nido‐[(Cp*M)2 B2 H2 E2 ], 1–4 (1: E = S; 2: E = Se, M = Co; 3 and 4: E = Se, M = Rh and Ir, respectively) in moderate‐to‐good yields. The solid‐state structures of these compounds show open‐cage triple‐decker clusters. Attempts to isolate the Te analogue have failed; however, in the case of cobalt, we have isolated an 11 skeletal‐electron‐pair nido‐[(Cp*Co)2 B5 H5 Te2 ], 5. The X‐ray diffraction structure of 5 shows monocapped square antiprismatic geometry, with two Te atoms in the core. To close the central four‐membered B2 E2 open ring of nido‐1 and nido‐2, we have performed a reaction with [Ru3 (CO)12 ], which leads to the formation of closo‐[(Cp*Co){µ‐η5 :η5 ‐B2 H2 E2 M}M{µ‐Ru(CO)4 }], 6 and 7 [6: E = S; 7: E = Se; M = Ru(CO)2 ]. In contrast, the reactions of nido‐2 and nido‐3 with [Fe2 (CO)9 ] result in heterometallic clusters nido‐[(Cp*M)Fe(CO)3 B2 H2 Se2 ], 8 and 9 (8: M = Co; 9: M = Rh), [(Cp*Co)Fe3 (CO)8 Se2 ], 10, and [(Cp*Co)Fe2 (CO)7 Se], 11. As nido‐8 also contains a four‐membered open ring B2 Se2 , we have treated this with [Ru3 (CO)12 ], which yields closo‐[(Cp*Co){µ‐η5 :η5 ‐B2 H2 Se2 M}M{µ‐Fe(CO)4 }], 12 [M = Ru(CO)2 ], which is analogous to that of 7. In addition, we have analyzed the divergence in the reactivity of nido‐[(Cp*M)2 B2 H2 E2 ], 2–4, with the help of density functional theory calculations. [ABSTRACT FROM AUTHOR]- Published
- 2018
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