Synthesis, X-ray structures and reactivity of the first bis(amino)metallastibanes and bis(amino)metallabismuthanes

The reaction of Me2Si(N-t-Bu)2ECl (E = Sb, Bi) with NaM(CO)nCp (M = Fe, Mo, W; Cp = ?5-C5H5) affords metallastibanes and bismuthanes, Cp(CO)nME(N-t-Bu)2SiMe2 (4a-c, 5a-c). The structures of 4c (E = Sb, M = W) and 5c (E = Bi, M = W) have been determined by X-ray crystallography. Both compounds are isotypic and isostructural and crystallize in the triclinic space group with a = 7.030 (9) A°, b = 10.51 (1) A°, c = 16.22 (2) A°, a = 94.1 (1)°, ß = 90.4 (1)°, ? = 104.9 (1)°, Z = 2 for 4c and a = 7.014 (9) A°, b = 10.57 (1) A°, c = 16.25 (2) A°, a = 94.1 (1)°, ß= 90.1 (1)°, ? = 104.6 (1)°, Z = 2 for 5c. The E-W s-bond lengths are 3.010 (1) A° for E = Sb and 3.082 (1) A° for E = Bi. The reaction of the antimony derivatives with Fe2(CO)9 yields [Fe(CO)4]Cp(CO)nMSb(N-t-Bu)2SiMe2 (6a-c) as a result of the complexation of the antimony lone pair. The crystal structures of 6a (M = Fe) and 6b (M = Mo) have been determined. 6a crystallizes in the monoclinic space group with a = 10.399 (9) A°, b = 16.76 (2) A°, c = 15.74 (1) A°, ß = 94.16 (6)°, and Z = 4. Both Sb-Fe bond lengths are almost similar: 2.547 (1) A° for the covalent bond and 2.530 (1) A° for the dative bond. 6b crystallizes in the monoclinic space group with a = 12.305 (7) A°, b = 13.812 (7) A°, c = 16.75 (1) A°, ß = 99.03 (5)°, and Z = 4. The Sb-Mo covalent bond length is 2.871 (1) A° and the Sb-Fe dative bond 2.539 (1) A°

Metallophospha-alkenes: a simple access and some reactivities involving the phosphorus atom

The synthesis and studies on the reactive behaviour of metallophospha-alkenes are reported

Main Group Element Transition Metal Multiple Bonds, IV. Catalytic Assistance by [Cp(CO)3_3Mo]2_2 in the Aggregation of Metalloarsines via Arsenic Metal Double Bond Complexes

The metallo-arsanes CP(CO)$_3$M - AsMc$_2$ (1 a, b) (M = Mo, W) are convcrted to the double arsenido-bridged dinuclear complexes [(η-AsMe$_2$)Mo(CO)$_2$Cp]$_2$ (3a, b) in the presence of [CP(CO)$_3$Mo]$_2$. Due to the unusual mild conditions of aggregation the intermediate formation of the double bonded species Cp(CO)$_2$M = AsMe$_2$ (2a, b) is postulated. The crystal structure of 3a is reported, which shows mutual trans arrangement of the cyclopentadienyl and CO ligands

Unusual structural features of a siloxane

Crystals of the R, S diastereoisomer of [Cp(CO)$_2$-FeSiCH$_3$F]$_2$O are monoclinic, space group ndc (No. 14), with a = 846.0(3) [836.4(1»), b = 768.0(3) [757.1(1»), c = 1548.5(4) [1522.3(2)] pm, {3 = 97.34(3t [97.47(3t] at 300 K [120 K] with Z = 2. Even at 120 K the Si-O-Si fragment is found to be strictly linear due to crystallographically imposed symmetry. To explain the unusual electron distribution derived from the X-ray data collected, several types of possible disorders are discussed, none of which leads to a satisfying explanation. Retaining the Ci symmetry (linear Si-O-Si fragment in the final model) the important bond lengths are Fe-Si 226.7(1) [226.5(1)] pm, Si-F 160.9(2) [161.8(2)] pm, Si-O 160.3(1) [161.1(1)] pm, Si-C 185.0(3) [185.6(3)] pm. The electronic features of this compound were probed via molecular orbital calculations of the extended Hiickel type. It was found that the lone pairs on the siloxane oxygen were tipped away from cylindrical symmetry. The tipping was directed toward the fluorine substituents on the silicon atoms and away from the CpFe(CO)$_2$ units. A pertubational approach was utilized to rationalize this effect