TY - JOUR
T1 - Triple-decker complex CpCo(μ-C3B2Me 5)Rh(C2H4)2
T2 - Synthesis, structure and bonding
AU - Romanov, A.S.
AU - Muratov, D.V.
AU - Timofeeva, T.V.
AU - Kudinov, A.R.
PY - 2014
Y1 - 2014
N2 - Abstract
The reaction of the thallium derivative [CpCo(μ-C3B2Me5)]Tl with [Rh(C2H4)2Cl]2 affords the μ-diborolyl bis(ethylene) triple-decker complex CpCo(μ-C3B2Me5)Rh(C2H4)2 (4). Structure of 4 was determined by X-ray diffraction. According to DFT calculations, the ethylene dissociation energies for the triple-decker complexes CpCo(μ-C3B2R5)Rh(C2H4)2 (R = H, Me) are ca. 6 kcal mol−1 lower than for cyclopentadienyl analogs (C5R5)Rh(C2H4)2. Energy decomposition analysis revealed that the bonding of anions [CpCo(C3B2R5)]− with [Rh(C2H4)2]+ is also weaker than that of [C5R5]−; the attractive interactions in both cases are 60–63% electrostatic and 37–40% covalent. The electrostatic potentials at the Rh nuclei suggest that the donor ability of the anions increases in the following order: Cp < [CpCo(C3B2H5)] ⩽ [CpCo(C3B2Me5)] < Cp∗.
Graphical abstract
The triple-decker complex CpCo(µ-C3B2Me5)Rh(C2H4)2 (4) was synthesized with high yield and structurally characterized. DFT calculation shows that Rh–C2H4 bonding in 4 is 10 kcal mol–1 weaker compared to CpRh(C2H4)2.
AB - Abstract
The reaction of the thallium derivative [CpCo(μ-C3B2Me5)]Tl with [Rh(C2H4)2Cl]2 affords the μ-diborolyl bis(ethylene) triple-decker complex CpCo(μ-C3B2Me5)Rh(C2H4)2 (4). Structure of 4 was determined by X-ray diffraction. According to DFT calculations, the ethylene dissociation energies for the triple-decker complexes CpCo(μ-C3B2R5)Rh(C2H4)2 (R = H, Me) are ca. 6 kcal mol−1 lower than for cyclopentadienyl analogs (C5R5)Rh(C2H4)2. Energy decomposition analysis revealed that the bonding of anions [CpCo(C3B2R5)]− with [Rh(C2H4)2]+ is also weaker than that of [C5R5]−; the attractive interactions in both cases are 60–63% electrostatic and 37–40% covalent. The electrostatic potentials at the Rh nuclei suggest that the donor ability of the anions increases in the following order: Cp < [CpCo(C3B2H5)] ⩽ [CpCo(C3B2Me5)] < Cp∗.
Graphical abstract
The triple-decker complex CpCo(µ-C3B2Me5)Rh(C2H4)2 (4) was synthesized with high yield and structurally characterized. DFT calculation shows that Rh–C2H4 bonding in 4 is 10 kcal mol–1 weaker compared to CpRh(C2H4)2.
UR - http://www.scopus.com/inward/record.url?eid=2-s2.0-84897502089&partnerID=MN8TOARS
U2 - 10.1016/j.ica.2014.02.033
DO - 10.1016/j.ica.2014.02.033
M3 - Article
SN - 0020-1693
VL - 415
SP - 120
EP - 123
JO - Inorganica Chimica Acta
JF - Inorganica Chimica Acta
ER -