OMS, OM(η²-SO), and OM(η²-SO)(η²-SO₂) Molecules (M = Ti, Zr, Hf): Infrared Spectra and Density Functional Calculations

Abstract

Infrared spectra of the matrix isolated OMS, OM(η(2)-SO), and OM(η(2)-SO)(η(2)-SO(2)) (M = Ti, Zr, Hf) molecules were observed following laser-ablated metal atom reactions with SO(2) during condensation in solid argon and neon. The assignments for the major vibrational modes were confirmed by appropriate S(18)O(2) and (34)SO(2) isotopic shifts, and density functional vibrational frequency calculations (B3LYP and BPW91). Bonding in the initial OM(η(2)-SO) reaction products and in the OM(η(2)-SO)(η(2)-SO(2)) adduct molecules with unusual chiral structures is discussed.

Spontaneous sulfur dioxide activation by Group V metal (V, Nb, Ta) atoms in excess argon at cryogenic temperatures

“…Similarities were also found between the 2 A state complex OM(Z 2 -SO) (M = V, Nb, Ta) and their counterparts in the reactions of Group IV metal atoms with SO 2 . 22 Calculations were also done for the OM(Z 2 -SO)(Z 2 -SO 2 ) and SMO 2 (SO 2 ) complexes, which are the SO 2 subunit coordinated to OM(Z 2 -SO) and SMO 2 molecules. Finally the triatomic molecule intermediates SMO were computed.…”

“…[16][17][18][19][20][21] Until recently, the behavior of Group IV (Ti, Zr, Hf) and Group VI (Cr, Mo, W) and U metal atom reactions with SO 2 have been investigated. [22][23][24] Metal oxide complexes OM(Z 2 -SO) (M = Ti, Zr, Hf) and metal sulfide oxides SMO 2 (M = Cr, Mo, W, U) have been identified in neon and argon matrices using vibrational IR spectroscopy and reproduced using theoretical calculations. The minor products OM(Z 2 -SO)(Z 2 -SO 2 ) (M = Ti, Zr, Hf) and (SO 2 )(SMO 2 ) (M = Cr, Mo, W, U) have also been reported.…”

Rationalizing the Low‐Spin Products Observed for the Reactions M+CH3CN (M=V, Nb,Ta) Through a Non‐Spin Flip Scheme.

“…Different reactions of laser‐ablated transition metal atoms with small organic molecules have been investigated under matrix‐isolation conditions by IR spectroscopy . The results emerging from these studies point toward new synthesis routes for obtaining high‐oxidation state products, such as those arising from the oxidative addition of the organic molecule to the metal atom, as well as carbene and carbyne compounds.…”

Reactions of Ti, Zr, and Hf Atoms with Hydrogen Sulfide: Argon Matrix Infrared Spectra and Theoretical Calculations

“…29,31 Laser-ablated Ti, Zr, and Hf atoms were reacted with H 2 S, H 2 34 S, and D 2 S in excess argon (4 K) during condensation by means of a closed-cycle helium refrigerator (SHI, SRDK-408D2). The H 2 S, H 2 34 S, and D 2 S samples were prepared by previously described method.…”