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Photochemistry of bis-{chloro(dicarbonyl)rhodium} in low temperature frozen gas matrices at 12 K and in Nujol mulls at 77 K: infrared and electronic spectroscopic evidence for retention of the bis-{(chloro)rhodium} bridging unit but photoejection of terminal carbonyl ligands

Authors
Journal
Journal of Organometallic Chemistry
0022-328X
Publisher
Elsevier
Publication Date
Volume
554
Issue
1
Identifiers
DOI: 10.1016/s0022-328x(97)00602-5
Keywords
  • Bis-{Chloro(Dicarbonyl)Rhodium}
  • Terminal Carbonyl Ligands
  • Uv–Visible
Disciplines
  • Chemistry

Abstract

Abstract Infrared and electronic spectroscopic evidence is presented in relation to the photochemical reactions of {(Cl)(CO) 2Rh} 2, whose bent structure has been confirmed by Fourier transform Raman spectroscopy. Photolysis in Ar, CH 4 and N 2 gas matrices at ca. 12 K and in Nujol mulls at ca. 77 K leads to facile and reversible ejection of the terminal CO ligands but retention of the {(Cl)Rh} 2 bridging unit. The primary species formed were Rh 2(Cl) 2(CO) 3 in Ar, CH 4 and Nujol media and Rh 2(Cl) 2(CO) 3(N 2) in N 2 matrices. Further reversible CO loss afforded {Rh(Cl)(CO)} 2 and {Rh(Cl)(CO)(N 2)} 2, respectively. In CO matrices the modest photoreaction was interpreted in terms of CO addition to give an 18 electron dimeric species {Rh(Cl)(CO) 3} 2 rather than bridge cleavage to give the 16 electron species Rh(Cl)(CO) 3. In view of the facility of the CO ejection/recombination processes it is suggested that such reaction pathways could be important in the substitution reactions of {Rh(Cl)(CO) 2} 2 and could aid the interpretation of the kinetic data.

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