13 C MAS NMR spectrum of polycrystalline [Rh(Acac)(CO)2] (1) displays separate signals from all 7... more 13 C MAS NMR spectrum of polycrystalline [Rh(Acac)(CO)2] (1) displays separate signals from all 7 carbon atoms: 2 doublets from CO ligand carbons along with 5 singlets from Acac carbons. GIPAW calculation of 13 C shielding tensor values also revealed nonequivalence of all carbon atoms in molecule 1 in the anisotropic medium of the crystal lattice. Apparently, the C2v symmetry of molecule 1 is broken owing to the asymmetry of its contacts to the neighboring molecules. For example, the contacts O···H–C of two CO ligands of molecule 1 to the CH group of the closest molecule in the adjacent stack are markedly different: the distances OH are 2.72 and 4.38 Å, OC are 3.65 and 5.00 Å, the angles OHC are 164.9° and 126.4°.
Acta Crystallographica Section C Structural Chemistry, 2016
Vaska-type complexes,i.e. trans-[RhX(CO)(PPh3)2] (Xis a halogen or pseudohalogen), undergo a rang... more Vaska-type complexes,i.e. trans-[RhX(CO)(PPh3)2] (Xis a halogen or pseudohalogen), undergo a range of reactions and exhibit considerable catalytic activity. The electron density on the RhIatom in these complexes plays an important role in their reactivity. Many cyanotrihydridoborate (BH3CN−) complexes of Group 6–8 transition metals have been synthesized and structurally characterized, an exception being the rhodium(I) complex. Carbonyl(cyanotrihydridoborato-κN)bis(triphenylphosphine-κP)rhodium(I), [Rh(NCBH3)(CO)(C18H15P)2], was prepared by the metathesis reaction of sodium cyanotrihydridoborate withtrans-[RhCl(CO)(PPh3)2], and was characterized by single-crystal X-ray diffraction analysis and IR,1H,13C and11B NMR spectroscopy. The X-ray diffraction data indicate that the cyanotrihydridoborate ligand coordinates to the RhIatom through the N atom in atransposition with respect to the carbonyl ligand; this was also confirmed by the IR and NMR data. The carbonyl stretching frequency ν(C...
A new rhodium(I) dimethyl sulfoxide (DMSO) 8-oxyquinolinato (Oxq) complex, [Rh(Oxq)(CO)(DMSO)] (I... more A new rhodium(I) dimethyl sulfoxide (DMSO) 8-oxyquinolinato (Oxq) complex, [Rh(Oxq)(CO)(DMSO)] (I), has been prepared and characterized by IR, 1 H and 13 C NMR, and X-ray data. DMSO is S-coordinated in the trans-N position. The values of n(CO), carbonyl d 13 S, as well as d 13 S and d 1 H of Oxq ligand for three L trans-N complexes, [RhOxq(CO)(L)] (L ¼ NH 3 , DMSO, and CO), define the intermediate position of DMSO within the ligand L series ranged in their net donating potency. Observed spinespin couplings of Oxq 13 C (C2, C3, C4a, C7, C8a) and 1 H (H2) nuclei to 103 Rh provide one more tool to study long-range interactions of Oxq rings with metallocenter and remote ligand L.
Trans-[RuPy4(CN)2 cleaves chloro-rhodium bridges in rhodium(I) binuclear complexes, [Rh(CO)2Cl]2,... more Trans-[RuPy4(CN)2 cleaves chloro-rhodium bridges in rhodium(I) binuclear complexes, [Rh(CO)2Cl]2, [Rh(Cod)Cl]2, and [(Cod)RhCl2Rh(CO)2] yielding heterometallic triad complexes, [(CO)2ClRh(NC)RuPy4(CN)RhCl(CO)2] (I), [(Cod)ClRh(NC)RuPy4(CN)RhCl(Cod)] (II), and [(Cod)ClRh(NC)RuPy4(CN)RhCl(CO)2] (III), respectively. In solutions, III coexists with equilibrium amounts of I and II in the near-binomial proportions. Under action of [Rh(CO)2Cl]2, II transforms into I with parallel formation of [Rh(Cod)Cl]2. Ligand effect transmission along the L-Rh-NC-Ru-CN-Rh-L′ chain is
Selective oxidation of one (trans to N) carbonyl group in [Rh(8-Oxiquinolinato)(CO) 2 ] with stoi... more Selective oxidation of one (trans to N) carbonyl group in [Rh(8-Oxiquinolinato)(CO) 2 ] with stoichiometric amount of Me 3 NO in MeCN produces a solution containing [Rh(Oxq)(CO)(Me 3 N)] and [Rh(Oxq)(CO)(MeCN)]. The ammonia complex, [Rh(Oxq)-(CO)(NH 3)], has been prepared by action of NH 3 gas on this solution and characterized by IR, 1 H and 13 C NMR, and X-ray data. Spectral parameters, m(CO), d 13 C, and 1 J(CRh), were measured in situ for a series of complexes [Rh(Oxq)(CO)(L)] (L = NAlk 3 , Py, PBu 3 , PPh 3 , P(OPh) 3 , C 8 H 14) formed upon action of L on [Rh(Oxq)(CO)(NH 3)] in THF. A new m(CO) and d 13 C based scale of r-donor/p-acceptor properties of ligands L is proposed including NH 3 and CO as the natural endpoints.
C MAS NMR spectrum of polycrystalline [Rh(Acac)(CO) 2 ] (1) displays separate signals from all 7 ... more C MAS NMR spectrum of polycrystalline [Rh(Acac)(CO) 2 ] (1) displays separate signals from all 7 carbon atoms: 2 doublets from CO ligand carbons along with 5 singlets from Acac carbons. GIPAW calculation of 13 C shielding tensor values also revealed nonequivalence of all carbon atoms in molecule 1 in the anisotropic medium of the crystal lattice. Apparently, the C 2v symmetry of molecule 1 is broken owing to the asymmetry of its contacts to the neighboring molecules. For example, the contacts O•••H-C of two CO ligands of molecule 1 to the CH group of the closest molecule in the adjacent stack are markedly different: the distances OH are 2.72 and 4.38 Å, OC are 3.65 and 5.00 Å, the angles OHC are 164.9° and 126.4°.
13C MAS NMR spectrum of polycrystalline [Rh(Acac) (CO)2] (1) displays separate signals from all 7... more 13C MAS NMR spectrum of polycrystalline [Rh(Acac) (CO)2] (1) displays separate signals from all 7 carbon atoms: 2 doublets from CO ligand carbons along with 5 singlets from Acac carbons. GIPAW calculation of 13C shielding tensor values also revealed the non-equivalence of all carbon atoms in molecule 1 in the anisotropic medium of the crystal lattice. Apparently, the C2v symmetry of molecule 1 is broken owing to the asymmetry of its contacts to the neighboring molecules. For example, the contacts O...H-C of two CO ligands of molecule 1 to the CH group of the closest molecule in the adjacent stack are markedly different: the distances OH are 2.72 and 4.38 Å, the distances OC are 3.65 and 5.00 Å, the angles OHC are 164.9 and 126.4º.
13 C MAS NMR spectrum of polycrystalline [Rh(Acac)(CO)2] (1) displays separate signals from all 7... more 13 C MAS NMR spectrum of polycrystalline [Rh(Acac)(CO)2] (1) displays separate signals from all 7 carbon atoms: 2 doublets from CO ligand carbons along with 5 singlets from Acac carbons. GIPAW calculation of 13 C shielding tensor values also revealed nonequivalence of all carbon atoms in molecule 1 in the anisotropic medium of the crystal lattice. Apparently, the C2v symmetry of molecule 1 is broken owing to the asymmetry of its contacts to the neighboring molecules. For example, the contacts O···H–C of two CO ligands of molecule 1 to the CH group of the closest molecule in the adjacent stack are markedly different: the distances OH are 2.72 and 4.38 Å, OC are 3.65 and 5.00 Å, the angles OHC are 164.9° and 126.4°.
Acta Crystallographica Section C Structural Chemistry, 2016
Vaska-type complexes,i.e. trans-[RhX(CO)(PPh3)2] (Xis a halogen or pseudohalogen), undergo a rang... more Vaska-type complexes,i.e. trans-[RhX(CO)(PPh3)2] (Xis a halogen or pseudohalogen), undergo a range of reactions and exhibit considerable catalytic activity. The electron density on the RhIatom in these complexes plays an important role in their reactivity. Many cyanotrihydridoborate (BH3CN−) complexes of Group 6–8 transition metals have been synthesized and structurally characterized, an exception being the rhodium(I) complex. Carbonyl(cyanotrihydridoborato-κN)bis(triphenylphosphine-κP)rhodium(I), [Rh(NCBH3)(CO)(C18H15P)2], was prepared by the metathesis reaction of sodium cyanotrihydridoborate withtrans-[RhCl(CO)(PPh3)2], and was characterized by single-crystal X-ray diffraction analysis and IR,1H,13C and11B NMR spectroscopy. The X-ray diffraction data indicate that the cyanotrihydridoborate ligand coordinates to the RhIatom through the N atom in atransposition with respect to the carbonyl ligand; this was also confirmed by the IR and NMR data. The carbonyl stretching frequency ν(C...
A new rhodium(I) dimethyl sulfoxide (DMSO) 8-oxyquinolinato (Oxq) complex, [Rh(Oxq)(CO)(DMSO)] (I... more A new rhodium(I) dimethyl sulfoxide (DMSO) 8-oxyquinolinato (Oxq) complex, [Rh(Oxq)(CO)(DMSO)] (I), has been prepared and characterized by IR, 1 H and 13 C NMR, and X-ray data. DMSO is S-coordinated in the trans-N position. The values of n(CO), carbonyl d 13 S, as well as d 13 S and d 1 H of Oxq ligand for three L trans-N complexes, [RhOxq(CO)(L)] (L ¼ NH 3 , DMSO, and CO), define the intermediate position of DMSO within the ligand L series ranged in their net donating potency. Observed spinespin couplings of Oxq 13 C (C2, C3, C4a, C7, C8a) and 1 H (H2) nuclei to 103 Rh provide one more tool to study long-range interactions of Oxq rings with metallocenter and remote ligand L.
Trans-[RuPy4(CN)2 cleaves chloro-rhodium bridges in rhodium(I) binuclear complexes, [Rh(CO)2Cl]2,... more Trans-[RuPy4(CN)2 cleaves chloro-rhodium bridges in rhodium(I) binuclear complexes, [Rh(CO)2Cl]2, [Rh(Cod)Cl]2, and [(Cod)RhCl2Rh(CO)2] yielding heterometallic triad complexes, [(CO)2ClRh(NC)RuPy4(CN)RhCl(CO)2] (I), [(Cod)ClRh(NC)RuPy4(CN)RhCl(Cod)] (II), and [(Cod)ClRh(NC)RuPy4(CN)RhCl(CO)2] (III), respectively. In solutions, III coexists with equilibrium amounts of I and II in the near-binomial proportions. Under action of [Rh(CO)2Cl]2, II transforms into I with parallel formation of [Rh(Cod)Cl]2. Ligand effect transmission along the L-Rh-NC-Ru-CN-Rh-L′ chain is
Selective oxidation of one (trans to N) carbonyl group in [Rh(8-Oxiquinolinato)(CO) 2 ] with stoi... more Selective oxidation of one (trans to N) carbonyl group in [Rh(8-Oxiquinolinato)(CO) 2 ] with stoichiometric amount of Me 3 NO in MeCN produces a solution containing [Rh(Oxq)(CO)(Me 3 N)] and [Rh(Oxq)(CO)(MeCN)]. The ammonia complex, [Rh(Oxq)-(CO)(NH 3)], has been prepared by action of NH 3 gas on this solution and characterized by IR, 1 H and 13 C NMR, and X-ray data. Spectral parameters, m(CO), d 13 C, and 1 J(CRh), were measured in situ for a series of complexes [Rh(Oxq)(CO)(L)] (L = NAlk 3 , Py, PBu 3 , PPh 3 , P(OPh) 3 , C 8 H 14) formed upon action of L on [Rh(Oxq)(CO)(NH 3)] in THF. A new m(CO) and d 13 C based scale of r-donor/p-acceptor properties of ligands L is proposed including NH 3 and CO as the natural endpoints.
C MAS NMR spectrum of polycrystalline [Rh(Acac)(CO) 2 ] (1) displays separate signals from all 7 ... more C MAS NMR spectrum of polycrystalline [Rh(Acac)(CO) 2 ] (1) displays separate signals from all 7 carbon atoms: 2 doublets from CO ligand carbons along with 5 singlets from Acac carbons. GIPAW calculation of 13 C shielding tensor values also revealed nonequivalence of all carbon atoms in molecule 1 in the anisotropic medium of the crystal lattice. Apparently, the C 2v symmetry of molecule 1 is broken owing to the asymmetry of its contacts to the neighboring molecules. For example, the contacts O•••H-C of two CO ligands of molecule 1 to the CH group of the closest molecule in the adjacent stack are markedly different: the distances OH are 2.72 and 4.38 Å, OC are 3.65 and 5.00 Å, the angles OHC are 164.9° and 126.4°.
13C MAS NMR spectrum of polycrystalline [Rh(Acac) (CO)2] (1) displays separate signals from all 7... more 13C MAS NMR spectrum of polycrystalline [Rh(Acac) (CO)2] (1) displays separate signals from all 7 carbon atoms: 2 doublets from CO ligand carbons along with 5 singlets from Acac carbons. GIPAW calculation of 13C shielding tensor values also revealed the non-equivalence of all carbon atoms in molecule 1 in the anisotropic medium of the crystal lattice. Apparently, the C2v symmetry of molecule 1 is broken owing to the asymmetry of its contacts to the neighboring molecules. For example, the contacts O...H-C of two CO ligands of molecule 1 to the CH group of the closest molecule in the adjacent stack are markedly different: the distances OH are 2.72 and 4.38 Å, the distances OC are 3.65 and 5.00 Å, the angles OHC are 164.9 and 126.4º.
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13C shielding tensor values also revealed the non-equivalence of all carbon atoms in molecule 1 in the anisotropic medium of the crystal lattice. Apparently, the C2v symmetry of molecule 1 is broken owing to the asymmetry of its contacts to the neighboring molecules. For example, the contacts O...H-C of two CO ligands of molecule 1 to the CH group of the closest molecule in the adjacent stack are markedly different: the distances OH are 2.72 and 4.38 Å, the distances OC are 3.65 and 5.00 Å, the angles OHC are 164.9 and 126.4º.
13C shielding tensor values also revealed the non-equivalence of all carbon atoms in molecule 1 in the anisotropic medium of the crystal lattice. Apparently, the C2v symmetry of molecule 1 is broken owing to the asymmetry of its contacts to the neighboring molecules. For example, the contacts O...H-C of two CO ligands of molecule 1 to the CH group of the closest molecule in the adjacent stack are markedly different: the distances OH are 2.72 and 4.38 Å, the distances OC are 3.65 and 5.00 Å, the angles OHC are 164.9 and 126.4º.