Some Novel Binuclear Group 13 Metal Tin Hydrides Formed in Ar Matrices Following the Codeposition of the Metal Vapor with SnH<sub>4</sub>

Gaertner, Benjamin; Himmel, Hans‐Jörg; MacRae, Vicky; Pardoe, Jennifer A. J.; Randall, Paul G.; Downs, Anthony J.

doi:10.1002/chem.200400564

Cited by 14 publications

(7 citation statements)

References 65 publications

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“…The reaction products in these two cases are believed to be Ga(m-SiH 3 )GaH with a terminal GaÀH bond and a bridging SiH 3 unit, [18] and the nido-type cluster Ga 2 Sn(m-H) 4 , respectively (see Figure 1). [19] This superior reactivity of Ga 2 is perhaps surprising since the GaÀGa bond in Ga 2 is quite weak (D 0 = ca. 110 kJ mol…”

Section: Introductionmentioning

confidence: 99%

Characterization of Isolated Ga₂ Molecules by Resonance Raman Spectroscopy and Variations of GaGa Bonding

Himmel

Gaertner

2004

Chemistry A European J

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Isolated Ga2 dimers were characterized in an argon matrix with the aid of resonance Raman and UV/Vis spectroscopy. The resonance Raman spectra gave evidence of not only the nu(Ga-Ga) fundamental, but also four overtones. Each of the signals exhibits 69Ga/71Ga isotopic splitting leading to the triplet pattern characteristic of two equivalent Ga atoms. On the basis of the experimental data, a harmonic frequency and anharmonicity constant have been determined for Ga2. An estimate of the dissociation energy on the assumption of a Morse-type potential energy curve results in a De value (upper limit) of about 145 kJ mol(-1). The force constant (64.8+/-0.3 N m(-1)) and dissociation energy of Ga2 are compared with those of other diatomics and those of molecules featuring Ga-Ga bonds.

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Section: Introductionmentioning

confidence: 99%

Characterization of Isolated Ga₂ Molecules by Resonance Raman Spectroscopy and Variations of GaGa Bonding

Himmel

Gaertner

2004

Chemistry A European J

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“…A more detailed account of the matrix reactivity of M 2 dimers toward SiH 4 and related molecules must, however, await the results of continuing research. [44] …”

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confidence: 99%

Matrix Reactivity of Al and Ga Atoms (M) in the Presence of Silane: Generation and Characterization of the η²‐Coordinated Complex M⋅SiH₄, the Insertion Product HMSiH₃, and the M^ISpecies MSiH₃in a Solid Argon Matrix

Gaertner

Himmel

MacRae

et al. 2004

Chemistry A European J

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Matrix isolation experiments give evidence for the formation of the loosely bonded metal-silane complex M.SiH(4) by the spontaneous reaction of Al or Ga atoms (M) with silane in a solid Ar matrix at 12 K; however, Ga(2) appears to insert spontaneously into an Si--H bond to form HGaGaSiH(3), probably with the structure HGa(micro-SiH(3))Ga. In M.SiH(4) the metal atom is eta(2)-coordinated by the silane, resulting in a species with C(2v) symmetry. The complex has a distinctive photochemistry: it can be converted on photolysis at lambda approximately 410 or approximately 254 nm to its tautomer, HMSiH(3), which also has a doublet ground electronic state and from which it can be regenerated with lambda approximately 580 nm radiation. Broadband UV-visible photolysis (lambda=200-800 nm) results in decomposition of HMSiH(3), the univalent species MSiH(3) being the only detectable product. The experimental data collected for several silane isotopomers (SiH(4), SiD(4), and SiD(3)H) and different reagent concentrations, together with the results of sophisticated quantum chemical calculations, are used to explore in detail the properties of the detected species and the reaction pathways compassing their formation.

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“…Al or Ga atoms will spontaneously insert into an Sn-H bond of SnH 4 to yield HMSnH 3 . 121 The Ga 2 dimer also inserts into such a bond to give Ga 2 (m-H) 4 Sn with a cubane-like structure. All of these products are photolabile; for example, HMSnH 3 tautomerises to H 2 M(m-H) 2 Sn.…”

Section: Group 13mentioning

confidence: 99%

Chemistry in low-temperature matrices

Almond

Goldberg

2007

Annu. Rep. Prog. Chem., Sect. C: Phys. Chem.

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the Progress of Chemistry, Section C. The report is divided into sections: weak adducts and conformational isomers; reactions of atoms; high-temperature molecules; photochemistry; biological molecules; astrochemistry. The last two sections reflect the fact that matrix isolation now extends into areas outside the traditional mainstream disciplines of chemistry. There are a number of areas where substantial progress has been made during the period of this report. First, the routine use of laser-ablation to generate atoms and to initiate atomic reactions in matrices has increased the scope of matrix isolation to synthesise many new molecular species in inorganic chemistry. Laser-ablation allows ground state atoms to be more easily studied than is the case when atoms are produced by thermal methods. Moreover, this procedure allows atoms to be generated from materials where thermal production is difficult. Secondly, the manufacture of more efficient closed-cycle helium refrigerators allows hydrogen matrices to be deposited readily. A significant body of work therefore has focussed upon metal hydrides, dihydrogen complexes and other hydrogen species in matrices. Underpinning all of this experimental work are theoretical calculations, without which the correct identification of most matrix isolation molecules would remain dangerously ambiguous. Infrared spectroscopy remains-as it has for the past 50 years-the workhorse of matrix isolation studies. It does seem that this situation will not change-it is impossible to conceive of another spectroscopic method that combines the necessary sensitivity to study molecules at very low dilution with the structural information required to make a reasonably certain identification.

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Some Novel Binuclear Group 13 Metal Tin Hydrides Formed in Ar Matrices Following the Codeposition of the Metal Vapor with SnH₄

Cited by 14 publications

References 65 publications

Characterization of Isolated Ga₂ Molecules by Resonance Raman Spectroscopy and Variations of GaGa Bonding

Characterization of Isolated Ga₂ Molecules by Resonance Raman Spectroscopy and Variations of GaGa Bonding

Matrix Reactivity of Al and Ga Atoms (M) in the Presence of Silane: Generation and Characterization of the η²‐Coordinated Complex M⋅SiH₄, the Insertion Product HMSiH₃, and the M^ISpecies MSiH₃in a Solid Argon Matrix

Chemistry in low-temperature matrices

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Some Novel Binuclear Group 13 Metal Tin Hydrides Formed in Ar Matrices Following the Codeposition of the Metal Vapor with SnH4

Cited by 14 publications

References 65 publications

Characterization of Isolated Ga2 Molecules by Resonance Raman Spectroscopy and Variations of GaGa Bonding

Characterization of Isolated Ga2 Molecules by Resonance Raman Spectroscopy and Variations of GaGa Bonding

Matrix Reactivity of Al and Ga Atoms (M) in the Presence of Silane: Generation and Characterization of the η2‐Coordinated Complex M⋅SiH4, the Insertion Product HMSiH3, and the MISpecies MSiH3in a Solid Argon Matrix

Chemistry in low-temperature matrices

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Some Novel Binuclear Group 13 Metal Tin Hydrides Formed in Ar Matrices Following the Codeposition of the Metal Vapor with SnH₄

Characterization of Isolated Ga₂ Molecules by Resonance Raman Spectroscopy and Variations of GaGa Bonding

Characterization of Isolated Ga₂ Molecules by Resonance Raman Spectroscopy and Variations of GaGa Bonding

Matrix Reactivity of Al and Ga Atoms (M) in the Presence of Silane: Generation and Characterization of the η²‐Coordinated Complex M⋅SiH₄, the Insertion Product HMSiH₃, and the M^ISpecies MSiH₃in a Solid Argon Matrix