Syntheses, Molecular Structures, and Vibrational Spectra of Chloropentacarbonylrhodium(III) and -iridium(III) Undecafluorodiantimonate(V), [Rh(CO)5Cl][Sb2F11]2
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- 作者：Helge Willner ; Christian Bach ; Rudolf Wartchow ; Changqing Wang ; Steven J. Rettig ; James Trotter ; Volker Jonas ; Walter Thiel ; and Friedhelm Aubke
- 刊名：Inorganic Chemistry
- 出版年：2000
- 出版时间：May 1, 2000
- 年：2000
- 卷：39
- 期：9
- 页码：1933 - 1942
- 全文大小：123K
- 年卷期：v.39,no.9(May 1, 2000)
- ISSN：1520-510X
文摘
The reactions of either bis(
-chloro)tetracarbonyldirhodium(I), [Rh(CO)2(-Cl)]2, or chlorotricarbonyliridium(I),[Ir(CO)3Cl]n, in the conjugate Br
nsted-Lewis superacid HF-SbF5 and in a CO atmosphere, produce [Rh(CO)5Cl][Sb2F11]2 or [Ir(CO)5Cl][Sb2F11]2, respectively. In these oxidative carbonylation reactions, antimony(V)fluoride functions as an oxidizing agent. The reduced product is identified as 6SbF3·5SbF5. [Rh(CO)5Cl][Sb2F11]2is obtained in the form of single crystals. Crystal data: monoclinic, space group P21 (No. 4); a = 9.721(1), b =12.602(1), c = 10.538(1) Å; 
= 106.51(1)
; V = 1237.7(2) Å3; Z = 2; T = 300 K; R1 [I > 3
(I)] = 0.0367, wR2= 0.0739. Single crystals of [Ir(CO)5Cl][Sb2F11]2 are produced in small amounts from a solution of mer-Ir(CO)3(SO3F)3 in magic acid, HSO3F-SbF5. The possible source of chlorine will be discussed. Crystal data for [Ir(CO)5Cl][Sb2F11]2: monoclinic, space group P21 (No. 4); a = 9.686(2), b = 12.585(2), c = 10.499(2) Å; =106.59(2); V = 1226.5(4) Å3; Z = 2; T = 294 K; R1[I > 3(I)] = 0.032, Rw = 0.031. The bond lengths andbond angles are nearly identical in the two isostructural salts; however, the cell volume of [Ir(CO)5Cl][Sb2F11]2is slightly smaller than that of [Rh(CO)5Cl][Sb2F11]2. The cations (point group C4v) feature unusually long M-Cbonds (M = Rh, Ir) and correspondingly short CO bonds, as well as high CO stretching wavenumbers and highCO stretching force constants. The [Sb2F11]- anions are not symmetry related, and their dihedral and bridgeangles differ slightly in both salts. There are significant interionic contacts in [Ir(CO)5Cl][Sb2F11]2 exclusively ofthe C- -F type (about 2 for each C atom of the five carbonyl groups) resulting in extended structures. The vibrationalspectra for both [M(CO)5Cl]2+ cations (M = Rh, Ir) are assigned with the help of density functional calculations,which also provide intensities for IR and Raman bands. While [Rh(CO)5Cl]2+ is the first cationic carbonyl derivativeof Rh(III), the vibrational and structural parameters for [Ir(CO)5Cl]2+ are compared to data for [Ir(CO)6]3+ andmer-Ir(CO)3(SO3F)3.
-chloro)tetracarbonyldirhodium(I), [Rh(CO)2(-Cl)]2, or chlorotricarbonyliridium(I),[Ir(CO)3Cl]n, in the conjugate Brnsted-Lewis superacid HF-SbF5 and in a CO atmosphere, produce [Rh(CO)5Cl][Sb2F11]2 or [Ir(CO)5Cl][Sb2F11]2, respectively. In these oxidative carbonylation reactions, antimony(V)fluoride functions as an oxidizing agent. The reduced product is identified as 6SbF3·5SbF5. [Rh(CO)5Cl][Sb2F11]2is obtained in the form of single crystals. Crystal data: monoclinic, space group P21 (No. 4); a = 9.721(1), b =12.602(1), c = 10.538(1) Å; = 106.51(1); V = 1237.7(2) Å3; Z = 2; T = 300 K; R1 [I > 3(I)] = 0.0367, wR2= 0.0739. Single crystals of [Ir(CO)5Cl][Sb2F11]2 are produced in small amounts from a solution of mer-Ir(CO)3(SO3F)3 in magic acid, HSO3F-SbF5. The possible source of chlorine will be discussed. Crystal data for [Ir(CO)5Cl][Sb2F11]2: monoclinic, space group P21 (No. 4); a = 9.686(2), b = 12.585(2), c = 10.499(2) Å; =106.59(2); V = 1226.5(4) Å3; Z = 2; T = 294 K; R1[I > 3(I)] = 0.032, Rw = 0.031. The bond lengths andbond angles are nearly identical in the two isostructural salts; however, the cell volume of [Ir(CO)5Cl][Sb2F11]2is slightly smaller than that of [Rh(CO)5Cl][Sb2F11]2. The cations (point group C4v) feature unusually long M-Cbonds (M = Rh, Ir) and correspondingly short CO bonds, as well as high CO stretching wavenumbers and highCO stretching force constants. The [Sb2F11]- anions are not symmetry related, and their dihedral and bridgeangles differ slightly in both salts. There are significant interionic contacts in [Ir(CO)5Cl][Sb2F11]2 exclusively ofthe C- -F type (about 2 for each C atom of the five carbonyl groups) resulting in extended structures. The vibrationalspectra for both [M(CO)5Cl]2+ cations (M = Rh, Ir) are assigned with the help of density functional calculations,which also provide intensities for IR and Raman bands. While [Rh(CO)5Cl]2+ is the first cationic carbonyl derivativeof Rh(III), the vibrational and structural parameters for [Ir(CO)5Cl]2+ are compared to data for [Ir(CO)6]3+ andmer-Ir(CO)3(SO3F)3.