Synthesis, Reactivity, and Stability of Di- and Trivalent Samarium Amides
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- 作者：Ravinder K. Minhas ; Yinlin Ma ; Jae-Inh Song ; and Sandro Gambarotta
- 刊名：Inorganic Chemistry
- 出版年：1996
- 出版时间：March 27, 1996
- 年：1996
- 卷：35
- 期：7
- 页码：1866 - 1873
- 全文大小：270K
- 年卷期：v.35,no.7(March 27, 1996)
- ISSN：1520-510X
文摘
SmCl3(THF)3 (THF =tetrahydrofuran) reacts with anionic dialkylamidesR2N- [R = Cy (cyclohexyl),i-Pr(isopropyl), Ph (phenyl)] to give different products, depending on thenature of the R substituents. Reaction withCy2NLi in a 1:2 molar ratio formed[(Cy2N)2Sm(
tities/mgr.gif">-Cl)(THF)]2(1) in 80% yield, whereas reaction with(i-Pr)2NLiunder similar conditions gave[(i-Pr2N)2SmCl3(Li(TMEDA))2](2). Partial loss of THF from complex 1reorganizedthe molecule into the tetranuclear(Cy2N)6Sm4Cl6(THF)2(3). Attempts to reduce complex 1 with anumber ofreagents gave[(Cy2N)3SmTHF]·toluene(5), while[(Cy2N)4SmLi(THF)] (4)was isolated upon alkylation reactionscarried out with either NpLi or NfLi [Np =CH2C(CH3)3; Nf =CH2C(CH3)2Ph]. Directsynthesis of Sm(II)amides from SmI2(THF)2 starting materialwas successful only in the case of diphenylamide anion(Ph2N-).Depending on the stoichiometry, -ate(Ph2N)4Sm[Na(TMEDA)]2(6) or neutral[(Ph2N)2Sm(THF)4]·THF(7) wasobtained. The crystal structures of 1-7were demonstrated by X-ray diffraction analysis. Crystal data areasfollows. 1:C56H105N4O2Sm2Cl2,triclinic, Ptities/onemacr.gif">, a = 14.344(1) Å,b = 23.897(2) Å, c = 10.2031(9)Å, 
=88.479(9)tities/deg.gif">, 
ta2.gif" BORDER=0 ALIGN="middle"> = 121.83(1)tities/deg.gif">, 
= 93.73(1)tities/deg.gif">,Z = 2. 2:C24H60N6SmCl3Li2triclinic, Ptities/onemacr.gif">, a = 11.552(1) Å,b =15.483(1) Å, c = 11.330(1) Å, =101.69(1)tities/deg.gif">, ta2.gif" BORDER=0 ALIGN="middle"> = 106.13(1)tities/deg.gif">, = 88.89(2)tities/deg.gif">.3:C80H148N6Cl6O2Sm4,triclinic,Ptities/onemacr.gif">, a = 16.508(1) Å, b= 16.7795(9) Å, c = 16.4030(8) Å, =89.794(1)tities/deg.gif">, ta2.gif" BORDER=0 ALIGN="middle"> = 88.688(2)tities/deg.gif">, =79.531(1)tities/deg.gif">,Z = 2. 4:C56H106N4O2LiSm,orthorhombic, Pna21, a =16.6145(9) Å, b = 17.5858(9) Å, c= 19.7754(9) Å,V = 5778.0(9) Å3, Z = 4.5:C47H82N3OSm, monoclinic,P21/c, a =10.250(2) Å, b = 23.305(2) Å, c =19.088(1) Å, ta2.gif" BORDER=0 ALIGN="middle"> = 100.90(1)tities/deg.gif">, Z = 4.6:C60H72N8SmNa2,tetragonal, I41/acd, a =18.0004(9) Å, c = 34.106(1) Å,Z= 8. 7:C44H60N2O5Sm,monoclinic, C2, a = 19.066(1) Å,b = 11.932(1) Å, c = 9.200(1) Å,ta2.gif" BORDER=0 ALIGN="middle"> = 93.89(1)tities/deg.gif">,Z = 2.
tities/mgr.gif">-Cl)(THF)]2(1) in 80% yield, whereas reaction with(i-Pr)2NLiunder similar conditions gave[(i-Pr2N)2SmCl3(Li(TMEDA))2](2). Partial loss of THF from complex 1reorganizedthe molecule into the tetranuclear(Cy2N)6Sm4Cl6(THF)2(3). Attempts to reduce complex 1 with anumber ofreagents gave[(Cy2N)3SmTHF]·toluene(5), while[(Cy2N)4SmLi(THF)] (4)was isolated upon alkylation reactionscarried out with either NpLi or NfLi [Np =CH2C(CH3)3; Nf =CH2C(CH3)2Ph]. Directsynthesis of Sm(II)amides from SmI2(THF)2 starting materialwas successful only in the case of diphenylamide anion(Ph2N-).Depending on the stoichiometry, -ate(Ph2N)4Sm[Na(TMEDA)]2(6) or neutral[(Ph2N)2Sm(THF)4]·THF(7) wasobtained. The crystal structures of 1-7were demonstrated by X-ray diffraction analysis. Crystal data areasfollows. 1:C56H105N4O2Sm2Cl2,triclinic, Ptities/onemacr.gif">, a = 14.344(1) Å,b = 23.897(2) Å, c = 10.2031(9)Å, =88.479(9)tities/deg.gif">, ta2.gif" BORDER=0 ALIGN="middle"> = 121.83(1)tities/deg.gif">, = 93.73(1)tities/deg.gif">,Z = 2. 2:C24H60N6SmCl3Li2triclinic, Ptities/onemacr.gif">, a = 11.552(1) Å,b =15.483(1) Å, c = 11.330(1) Å, =101.69(1)tities/deg.gif">, ta2.gif" BORDER=0 ALIGN="middle"> = 106.13(1)tities/deg.gif">, = 88.89(2)tities/deg.gif">.3:C80H148N6Cl6O2Sm4,triclinic,Ptities/onemacr.gif">, a = 16.508(1) Å, b= 16.7795(9) Å, c = 16.4030(8) Å, =89.794(1)tities/deg.gif">, ta2.gif" BORDER=0 ALIGN="middle"> = 88.688(2)tities/deg.gif">, =79.531(1)tities/deg.gif">,Z = 2. 4:C56H106N4O2LiSm,orthorhombic, Pna21, a =16.6145(9) Å, b = 17.5858(9) Å, c= 19.7754(9) Å,V = 5778.0(9) Å3, Z = 4.5:C47H82N3OSm, monoclinic,P21/c, a =10.250(2) Å, b = 23.305(2) Å, c =19.088(1) Å, ta2.gif" BORDER=0 ALIGN="middle"> = 100.90(1)tities/deg.gif">, Z = 4.6:C60H72N8SmNa2,tetragonal, I41/acd, a =18.0004(9) Å, c = 34.106(1) Å,Z= 8. 7:C44H60N2O5Sm,monoclinic, C2, a = 19.066(1) Å,b = 11.932(1) Å, c = 9.200(1) Å,ta2.gif" BORDER=0 ALIGN="middle"> = 93.89(1)tities/deg.gif">,Z = 2.