Synthesis, Structure, and Reactivity of Iodo-Functionalized Heterobimetallic Alkoxides of Tin(IV):  X-ray Crystal Structures of [I₂Sn{Al(OPrⁱ)₄}₂], [I₂Sn{Ti(OPrⁱ)₅}₂], [I₃Sn{Zr(OPrⁱ)₅(PrⁱOH)}], and [I₂Sn{Mo(C₅H₅)(CO)₃}₂]

Abstract

A series of new iodide heterobimetallic isopropoxides [I 2 Sn{Al(OPr i ) 4 } 2 ] (1), [I 2 Sn{Ti-(OPr i ) 5 } 2 ] (2), [I 2 Sn{Nb(OPr i ) 6 } 2 ] (3), and [I 3 Sn{Zr(OPr i ) 5 (Pr i OH)}] (4) obtained on reacting SnI 4 with stoichiometric amounts of alkali-metal reagents [KAl(OPr i ) 4 ] n , [KTi(OPr i ) 5 ] n , [KZr-(OPr i ) 5 ] n , and [KNb(OPr i ) 6 ] n , respectively, is reported. The monomeric formulation and hexacoordination of tin proposed for 1-4, on the basis of microanalytical, cryoscopic, and multinuclear ( 1 H, 13 C, 27 Al, and 119 Sn) NMR spectral data, was established for 1, 2, and 4 by single-crystal X-ray diffraction analysis. The solid-state structures of 1 and 2 feature an approximately octahedral tin(IV) center bearing two terminal iodide ligands and two bidentate {Al(OPr i ) 4 }and {Ti(OPr i ) 5 }moieties, containing aluminum or titanium atoms in a distorted tetrahedral or trigonal-bipyramidal environment of OPr i ligands, respectively. The crystal structure of 4 represents a bioctahedron formed by the face-sharing interaction of two slightly distorted octahedra built around Sn(IV) and Zr(IV) centers. Compounds 1 and 2, when allowed to react (1:2) with the transition-metal derivative Na[Mo(C 5 H 5 )(CO) 3 ], afford the Sn-Mo-bonded cluster [I 2 Sn{Mo(C 5 H 5 )(CO) 3 } 2 ] (5) as the only isolable product, in both the cases.

Structural characterization of the anionic halfsandwich complex and its reactivity towards stannanes and distannanes

“…By slow evaporation of a saturated solution of 2 in hexane suitable single crystals for X-ray diffraction were obtained. The molecule shows a four-legged piano-stool geometry with a large Mo-Sn distance of 2.8546(3) Å which is comparable to that of related molybdenum stannyl complexes such as ½fFeðg 5 -C 5 H 5 ÞðCOÞ 2 g 2 fMoðg 5 -C 5 H 5 ÞðCOÞ 3 gSnCl [22]. The SnMe 3 ligand adopts a staggered conformation with respect to the ½Moðg 5 -C 5 H 5 ÞðCOÞ 3 fragment as indicated by a dihedral angle Cp Cent -Mo-Sn-C6 of 175.39°.This orientation together with the large Mo-Sn separation allows for rather acute Sn-Mo-C(O) angles of 68.48(6) and 69.42 (8)°compared to the (O)C-Mo-C(O) angles of (79.30 (9) and 81.18(9)°).…”

“…While even commercially available as the sodium salt, an X-ray diffraction study has not been obtained so far on any complex M½Moðg 5 -C 5 H 5 ÞðCOÞ 3 . Various stannane complexes of molybdenum have been synthesized by reaction of organotin halides with this anion, leading not only to mono-but di-and even tri-nuclear tin compounds [22,23]. Mostly due to their early discovery in the sixties, the crystal structures of these were generally not established.…”

Iron(iii) and titanium(iv) oxoalkoxide chemistry: synthetic, structural, magnetochemical and spectroscopic studies of [Ti3(μ3-OPri)2(μ-OPri)3(OPri)6][FeCl4] and [Fe5(μ5-O)(μ-OPri)8Cl5]

“…4b The reaction between ''NaTi(OPr i ) 5 '' and FeCl 3 (2 : 1, route 2) was carried out in the absence of propan-2-ol, following a procedure described earlier by Veith and co-workers for the preparation of [SnI 2 {Ti(OPr i ) 5 } 2 ] and other heterometallic iodoisopropoxides. 16 Two crystalline iron-containing products were isolated, which were shown by X-ray diffraction analyses to be identical with B and C. No redox reaction was detected in this case and no complex A was obtained. This probably limited the amount of free chloride in solution, giving a much lower yield of B in route 2 than in route 1, as discussed below.…”

Tin(II) aminoalkoxides and heterobimetallic derivatives: the structures of Sn6(O)4(dmae)4, Sn6(O)4(OEt)4 and [Sn(dmae)2Cd(acac)2]2

“…24,25 Numerous heterobimetallic alkoxides containing tin are known, 1 which could serve as single-source precursors to M : SnO 2 composites, but these uniformly contain simple alkoxides, e.g. OEt, 26 OBu t , 27 -29 OPr i , 30,31 and, as a result, could suffer from disproportionation into separate homometallic components at elevated temperatures. To our knowledge, functionalised alkoxides, e.g.…”