TY - JOUR
T1 - Synthesis and molecular structure of mixed-metal stannylene derivatives of cyclopentadienyl(nitrosyl)(carbonyl) manganese
AU - Blokhin, Anton
AU - Pasynskii, Alexander
AU - Scheer, Manfred
AU - Virovets, Alexander
AU - Torubaev, Yury
N1 - Funding Information:
We gratefully acknowledge the financial support from the Russian Foundation for Basic Research (grant 12-03-33101a , 12-03-00860 ), Department of Chemistry and Material Sciences of RAS (grant OKh 1.3 ), Presidium of RAS (grant 8P21 ) and RF President Fellowship (MD 7122.2012.3).
PY - 2013/1/15
Y1 - 2013/1/15
N2 - The metathesis of CpMn(CO)(NO)SnCl3 (I) and anionic carbonyls (ML-) Mn(CO)5-, Co(CO)4-, Cp′Mo(CO)3-, Cp′W( CO)3-, Cp″Mo(CO)3- provided trinuclear mixed-metal complexes of general formula CpMn(CO)(NO)SnCl2ML (VIII-XII; Cp = C5H5, Cp′ = C5H4CH3, Cp″ = C 5H3(C4H9)2). Along with XII, the product of transmetallation Cp″Mo(CO)3SnCl3 (XIII) was separated. Interaction of I with Fe2( CO)82- gave the mixed-metal cluster Cp(CO)(NO)Mn-SnCl 2-Fe(CO)4-SnCl2-MnCp(CO)(NO) (XIV) which contain the pentanuclear metal-chain. As determined by the single crystal XRD analysis, the Mn-Sn distance in CpMn(CO)(NO)Sn fragment is 0.2 shorter than the expected value based on the Mn/Sn sum of covalent radii (SCR). From the other hand, the shortening of Sn-ML distances is in an accord with the donor ability of an ML fragment in the row Co(CO)4 ∼ Mn(CO)5 < Fe(CO)4 < CpMn(CO)(NO < Cp′Mo(CO)3 < Cp′W(CO)3 < Cp″Mo(CO)3 owing to the additive back donation of the transition metal d-LEP to Sn vacant orbitals. The absence of substantial elongation of the Sn-Cl distances may result from the π-back donation of transition metal d-orbitals to tin d-orbitals.
AB - The metathesis of CpMn(CO)(NO)SnCl3 (I) and anionic carbonyls (ML-) Mn(CO)5-, Co(CO)4-, Cp′Mo(CO)3-, Cp′W( CO)3-, Cp″Mo(CO)3- provided trinuclear mixed-metal complexes of general formula CpMn(CO)(NO)SnCl2ML (VIII-XII; Cp = C5H5, Cp′ = C5H4CH3, Cp″ = C 5H3(C4H9)2). Along with XII, the product of transmetallation Cp″Mo(CO)3SnCl3 (XIII) was separated. Interaction of I with Fe2( CO)82- gave the mixed-metal cluster Cp(CO)(NO)Mn-SnCl 2-Fe(CO)4-SnCl2-MnCp(CO)(NO) (XIV) which contain the pentanuclear metal-chain. As determined by the single crystal XRD analysis, the Mn-Sn distance in CpMn(CO)(NO)Sn fragment is 0.2 shorter than the expected value based on the Mn/Sn sum of covalent radii (SCR). From the other hand, the shortening of Sn-ML distances is in an accord with the donor ability of an ML fragment in the row Co(CO)4 ∼ Mn(CO)5 < Fe(CO)4 < CpMn(CO)(NO < Cp′Mo(CO)3 < Cp′W(CO)3 < Cp″Mo(CO)3 owing to the additive back donation of the transition metal d-LEP to Sn vacant orbitals. The absence of substantial elongation of the Sn-Cl distances may result from the π-back donation of transition metal d-orbitals to tin d-orbitals.
KW - Cyclopentadienyl complexes
KW - Manganese
KW - Metal carbonyl
KW - Metal-metal bond
KW - Tin
UR - http://www.scopus.com/inward/record.url?scp=84869880336&partnerID=8YFLogxK
U2 - 10.1016/j.jorganchem.2012.09.017
DO - 10.1016/j.jorganchem.2012.09.017
M3 - Article
AN - SCOPUS:84869880336
SN - 0022-328X
VL - 724
SP - 75
EP - 81
JO - Journal of Organometallic Chemistry
JF - Journal of Organometallic Chemistry
ER -