TY - JOUR

T1 - Structures and Stability of Molecular InBr3Pyx (x=1-3) Complexes: Unexpected Solid State Stabilization of Dimeric In2Br6Py4 As Compared to Valence-lsoelectronic Group 15 and 17 Halogen Bridging Dimers

AU - Kazakov, Igor V.

AU - Bodensteiner, Michael

AU - Lisovenko, Anna S.

AU - Suvorov, Andrew V.

AU - Scheer, Manfred

AU - Balazs, Gabor

AU - Timoshkin, Alexey Y.

PY - 2013

Y1 - 2013

N2 - Molecular structures of series of InBr3Pyx complexes (x = 1-3) in the solid state have been determined by single crystal structure analysis. For x = 2, an unexpected dimeric In2Br6Py4 structure, which features a nearly planar In2Br6 unit, has been established. This structure completes the series of known valence-isoelectronic dimeric molecules of group 17 (I2Cl6) and group 15 elements (As2Cl6 center dot 2PMe(3)). Theoretical studies at the B3LYP/def2-TZVP level of theory reveal that all gaseous M2X6Py4 dimers (M = Al, Ga, In, Tl; X = Cl, Br) are energetically unstable with respect to dissociation into MX3Py2 monomers. This finding is in stark contrast to the valence-isoelectronic group 17 and 15 analogs, which are predicted to be energetically stable with respect to dissociation. Thus, additional interactions in the solid state play a crucial role in stabilization of the experimentally observed dimeric In2Br6Py4. Thermal stability and volatility of InBr(3)Pyx complexes have been studied by tensimetry and mass

AB - Molecular structures of series of InBr3Pyx complexes (x = 1-3) in the solid state have been determined by single crystal structure analysis. For x = 2, an unexpected dimeric In2Br6Py4 structure, which features a nearly planar In2Br6 unit, has been established. This structure completes the series of known valence-isoelectronic dimeric molecules of group 17 (I2Cl6) and group 15 elements (As2Cl6 center dot 2PMe(3)). Theoretical studies at the B3LYP/def2-TZVP level of theory reveal that all gaseous M2X6Py4 dimers (M = Al, Ga, In, Tl; X = Cl, Br) are energetically unstable with respect to dissociation into MX3Py2 monomers. This finding is in stark contrast to the valence-isoelectronic group 17 and 15 analogs, which are predicted to be energetically stable with respect to dissociation. Thus, additional interactions in the solid state play a crucial role in stabilization of the experimentally observed dimeric In2Br6Py4. Thermal stability and volatility of InBr(3)Pyx complexes have been studied by tensimetry and mass

U2 - 10.1021/ic402162d

DO - 10.1021/ic402162d

M3 - Article

VL - 52

SP - 13207

EP - 13215

JO - Inorganic Chemistry

JF - Inorganic Chemistry

SN - 0020-1669

IS - 22

ER -