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Syntheses and vibrational and C-13 MAS-NMR spectra of bis(carbonyl)mercury(II) undecafluorodiantimonate(V) ([Hg(CO)(2)][Sb2F11](2)) and of bis(carbonyl) dimercury(I) undecafluorodiantimonate ([Hg-2(CO)(2)][Sb2F11](2)) and the molecular structure of [Hg(CO

TitleSyntheses and vibrational and C-13 MAS-NMR spectra of bis(carbonyl)mercury(II) undecafluorodiantimonate(V) ([Hg(CO)(2)][Sb2F11](2)) and of bis(carbonyl) dimercury(I) undecafluorodiantimonate ([Hg-2(CO)(2)][Sb2F11](2)) and the molecular structure of [Hg(CO
Publication TypeJournal Article
Year of Publication1996
AuthorsBodenbinder, M, Balzerjollenbeck, G, Willner, H, Batchelor, RJ, Einstein, FWB, Wang, C, Aubke, F
JournalInorganic Chemistry
Volume35
Pagination82-92
Date PublishedJan
Type of ArticleArticle
ISBN Number0020-1669
KeywordsACIDS, BOND, CARBON-MONOXIDE, CATIONS, CONSTANTS, CRYSTAL-STRUCTURES
Abstract

The synthesis of bis(carbonyl)mercury(II) undecafluorodiantimonate(V), [Hg(CO)(2)][Sb2F11](2), and that of the corresponding mercury(I) salt [Hg-2(CO)(2)][Sb2F11](2) are accomplished by the solvolyses of Hg(SO3F)(2) or of Hg2F2, treated with fluorosulfuric acid, HSO3F, in liquid antimony(V) fluoride at 80 or 60 degrees C, respectively, in an atmosphere of CO (500-800 mbar). The resulting white solids are the first examples of metal carbonyl derivatives formed by a post-transition element. Both salts are characterized by FT-IR, FT-Raman, and C-13-MAS-NMR spectroscopy. For [Hg(CO)(2)][Sb2F11], unprecedentedly high CO stretching frequencies (<(nu)over bar>(av) = 2279.5 cm(-1)) and stretching force constant (f(r) = 21.0 +/- 0.1) x 10(2) Nm(-1)) are obtained. Equally unprecedented is the (1)J(C-13-Hg-199) value of 5219 +/- 5 Hz observed in the C-13 MAS-NMR spectrum of the C-13 labeled isotopomers at delta = 168.8 +/- 0.1 ppm. The corresponding values (<(nu)over bar>(av) = 2247 cm(-1), f(r) = (20.4 +/- 0.1) x 10(2) Nm(-1), (1)J(C-13-Hg-199) = 3350 +/- 50 Hz and (2)J(C-13-Hg-199) 850 +/- 50 Hz) are found for [Hg-2(CO)(2)][Sb2F11](2), which has lower thermal stability (decomposition point in a sealed tube is 140 degrees C vs 160 degrees C for the Hg(II) compound) and a decomposition pressure of 8 Torr at 20 degrees C. The mercury(I) salt is sensitive toward oxidation to [Hg(CO)(2)][Sb2F11](2) during synthesis. Both linear cations (point group D infinity h) are excellent examples of nonclassical (sigma-only) metal-CO bonding. Crystal data for [Hg(CO)(2)][Sb2F11](2): monoclinic, space group P2(1)/n; Z = 2; a = 7.607(2) Angstrom; b = 14.001(3) Angstrom; c = 9.730(2) Angstrom; beta = 111.05(2)degrees; V = 957.1 Angstrom(3); T = 195 K; R(F) = 0.035 for 1983 data (I-0 greater than or equal to 2.5 sigma(I-0)) and 143 variables. The Hg atom lies on a crystallographic inversion center. The Hg-C-O angle is 177.7(7)degrees. The length of the mercury-carbon bond is 2.083(10) Angstrom and of the C-O bond 1.104(12) Angstrom respectively. The structure is stabilized in the solid state by a number of significant secondary interionic Hg–-F and C–-F contacts.

URL<Go to ISI>://A1996TP07200016