Activation of bis(guanidinate)lanthanide alkyl and aryl complexes on elemental sulfur: synthesis and characterization of bis(guanidinate)lanthanide thiolates and disulfides.
The treatment of [(Me(3)Si)(2)NC(NCy)(2)](2)Ln(mu-Cl)(2)Li(THF)(2) with 1 equiv of BnK (Bn = benzyl) in toluene affords [(Me(3)Si)(2)NC(NCy)(2)](2)LnBn [Ln = Er (1-Er), Y (1-Y)] in good yields. Similarly, [(Me(3)Si)(2)NC(NCy)(2)](2)Ln(t)Bu [Ln = Er (2-Er), Yb (2-Yb)] are obtained in satisfactory yields by the reaction of [(Me(3)Si)(2)NC(NCy)(2)](2)Ln(mu-Cl)(2)Li(THF)(2) with (t)BuLi in hexane. 1 reacts with 1/8 equiv of S(8) in toluene to form the sulfur insertion products {[(Me(3)Si)(2)NC(NCy)(2)](2)Ln(mu-SBn)}(2) [Ln = Er (3-Er), Y (3-Y)], while the reaction of 2 with elemental sulfur under the same conditions affords the oxidation products {[(Me(3)Si)(2)NC(NCy)(2)](2)Ln}(2)(mu-eta(2):eta(2)-S(2)) [Ln = Er (4-Er), Yb (4-Yb)] regardless of the equivalency of S(8) employed. Disulfide complexes 4 can also be obtained by the reaction of 3 with (1)/(4) equiv of S(8). Furthermore, the treatment of [(Me(3)Si)(2)NC(NCy)(2)](2)Ln(mu-Cl)(2)Li(THF)(2) with 1 equiv of (n)BuLi in hexane, followed by reaction with (1)/(8) equiv of S(8), affords the dinuclear thiolate complexes {[(Me(3)Si)(2)NC(NCy)(2)](2)Ln(mu-S(n)Bu)}(2) [Ln = Y (5-Y), Er (5-Er)] in good yields. However, under the same conditions, [(Me(3)Si)(2)NC(NCy)(2)](2)Yb(mu-Cl)(2)Li(THF)(2) reacts with (n)BuLi and S(8) to give {[(Me(3)Si)(2)NC(NCy)(2)](2)Yb}(2)(mu-eta(2):eta(2)-S(2)) (4-Yb) as the main metal-containing product. [(Me(3)Si)(2)NC(NCy)(2)](2)LnPh (generated in situ from [(Me(3)Si)(2)NC(NCy)(2)](2)Ln(mu-Cl)(2)Li(THF)(2) and PhLi) also undergoes sulfur insertion, affording {[(Me(3)Si)(2)NC(NCy)(2)](2)Ln(mu-SPh)}(2) [Ln = Er (6-Er), Yb (6-Yb)] in good yields. All of the complexes were characterized by spectroscopic and elemental analyses. The structures of all of these compounds, except 3-Y, are also determined by single-crystal X-ray diffraction analysis. Surprisingly, 3, 5, and 6 bear the same space group and very similar cell parameters, despite the different thiolate ligands.
Zhang
Zhengxing
Z
Molecular Catalysis and Innovative Material Laboratory, Department of Chemistry, Fudan University, Shanghai 200433, People's Republic of China.
Zhang
Lixin
L
Li
Yanrong
Y
Hong
Longcheng
L
Chen
Zhenxia
Z
Zhou
Xigeng
X
D018360:Crystallography, X-Ray; D004220:Disulfides / Q000737:chemistry*; D006146:Guanidines / Q000737:chemistry*; D028581:Lanthanoid Series Elements / Q000737:chemistry*; D008958:Models, Molecular; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000138:chemical synthesis* / Q000737:chemistry*; D013237:Stereoisomerism; D013438:Sulfhydryl Compounds / Q000737:chemistry*; D013455:Sulfur / Q000737:chemistry*
D004220:Disulfides; D006146:Guanidines; D028581:Lanthanoid Series Elements; D009942:Organometallic Compounds; D013438:Sulfhydryl Compounds; D013455:Sulfur