The Interaction of Disiloxane with Aluminum Halides<sup>1</sup>

Kriner, William A.; MacDiarmid, Alan G.; Evers, E. Charles

doi:10.1021/ja01540a009

Cited by 18 publications

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“…Several routes to SiFH3 exist, but they involve handling dangerous and/or difficult to synthesize starting materials. [25][26][27][28] The reaction between SiFBr3 and 3 equiv of Me3SnH resulted in the formation of SiH4 (60%), SiF2H2 (20%), and SiF3H (20%).…”

Section: Resultsmentioning

confidence: 99%

Selective and sequential reduction of polyhalosilanes with alkyltin hydrides

D'Errico¹,

Sharp²

1989

Inorg. Chem.

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2177v2-disulfides (Sl-S2CI, S3-S4) and an oxo ligand (01). This orientation is populated 87% of the time. In orientation b the disulfide S1X-S7 serves as a bridge the same way S8-S7 does in orientation a. In orientation b the ligand sites S2C1 and CllS are populated by a chloride and a sulfur atom, respectively. The dimer contains pseudo-seven-coordinate Mo(V1) ions. The ligands define a distorted-pentagonal-bipyramidal arrangement similar to the one observed in Intramolecular bond distances and angles in IV (Tables VI and VII) are ver similar to shorter than the one observed in the cis-mer pentagonal-bipyr-In this complex the Mo-CI distance associated with the equatorial chloride lies at 2.417 (1) A. In the same complex, the Mo-C1 bond across the axial oxo ligand at 2.504 (1) A is nearly 0.1 A longer than the Mo-CI,, bond. This is due to the strong trans effect of the oxo group.X-ray crystallography does not distinguish betwzen a chloride (CI-) ligand and a hydrosulfido (SH-) ligand. For this reason two formulations were considered: (a) [Mo2O2S8C1]-and (b) [Mo2O2S8SH]-. Formulation b would be analogous to the thiotungstate [(~-02,a'-S2)W2(S)2(v2-S2)~SH]-, [W2S,,H]-39 anion. those in 111. The Mo-C1, bond length at 2.388 (3) K is slightly (38) Dirand, J.; Ricard, L,.; Raymond, W. J . Chem. SOC., Dalton Trans. 278.Elemental analysis for chloride indicated that formulation a is the chemically correct one. Single-crystal structure determination of the iodo analogue, [ M O~O~S~I I -,~ obtained from the reaction of (Et4N)2[Mo202S9,14] with Ni12, shows that a halide substitution for a sulfide is indeed taking place. In the structure of the [M0202S81]2-anion ( R = 0.04) no disorder is encountered and, as in IV, the Mo coordination sphere geometry and the Mo-S and Mo=O bond lengths in this com lex are similar to those in 111. The Mo-I length is 2.766 (2) 1.Acknowledgment. The financial support of this project by the National Science Foundation is gratefully acknowledged.Note Added in Proof. Recently the synthesis and structural characterization of the Ta2SIl4-and Nb4Se226 anions were reported (Schreiner, S.; Aleandri, L. E.; Kang, D.; Ibers, J. A. Inorg. Chem. 1989,28, 392). These complexes are closely related structurally to the [Mo2O2S9I2-and [ Mo40,SI8l2-anions reported herein.Supplementary Material Available: Table S 1, listing thermal parameters and hydrogen atom positions for I, and Tables S2-S4, listing thermal parameters, hydrogen atom positions, and detailed bond distances and angles for 11-IV (24 pages); Tables S5-S8, listing observed and calculated structure factors for I-IV (48 pages). Ordering information is given on any current masthead page. (39) Secheresse, F.; Manoli, J. M.; Potvin, C.The reactions between alkyltin hydrides and a variety of polyhalo-and mixed halosilanes have been investigated. For SiCI, and SiCI3H, the reductions proceed in a stepwise manner to yield the monoreduced species as the major products. The reduction of SiBr, occurs much faster to yield a mixture of SiBr,H and SiH,, or, in the...

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Section: Resultsmentioning

confidence: 99%