Novel Stannatrane N(CH2CMe2O)2(CMe2CH2O)SnO-t-Bu and Related Oligonuclear Tin(IV) Oxoclusters. Two Isomers in One Crystal

The syntheses of the alkanolamine N­(CH2CMe2OH)2(CMe2CH2OH) (1), of the stannatrane N­(CH2CMe2O)2(CMe2CH2O)­SnO-t-Bu (2), and of the trinuclear tin oxocluster 3 consisting of the two isomers [(μ3-O)­(O-t-Bu)­{Sn­(OCH2CMe2)­(OCMe2CH2)2N}3] (3a) and [(μ3-O)­(μ3-O-t-Bu)­{Sn­(OCH2CMe2)­(OCMe2CH2)2N}3] (3b) as well as the isolation of a few crystals of the hexanuclear tin oxocluster [LSnOSn­(OH)3LSnOH]2 [L = N­(CH2CMe2O)2(CMe2CH2O)] (4) are reported. The compounds were characterized by 1H, 13C, 15N, and 119Sn (1–3) nuclear magnetic resonance and infrared spectroscopy, electrospray ionization mass spectrometry, and single-crystal X-ray diffraction analysis (1–4). A graph set analysis was performed for compound 1. The relative energies of 3a and 3b were estimated by density functional theory calculations that show that the energy differences are small.本文报道了烷醇胺N(CH₂C(CH₃)₂OH)₂(C(CH₃)₂CH₂OH)（化合物1）、锡杂笼状配合物（stannatrane）N(CH₂C(CH₃)₂O)₂(C(CH₃)₂CH₂O)-SnO-叔丁基（化合物2），以及由两种异构体[(μ₃-O)(O-叔丁基){Sn(OCH₂C(CH₃)₂)(OC(CH₃)₂CH₂)₂N}₃]（3a）和[(μ₃-O)(μ₃-O-叔丁基){Sn(OCH₂C(CH₃)₂)(OC(CH₃)₂CH₂)₂N}₃]（3b）组成的三核锡氧簇合物3的合成；同时还分离得到了六核锡氧簇合物[LSnOSn(OH)₃LSnOH]₂[L = N(CH₂C(CH₃)₂O)₂(C(CH₃)₂CH₂O)]（化合物4）的少量单晶。上述化合物通过¹H、¹³C、¹⁵N及¹¹⁹Sn（化合物1~3）核磁共振波谱、红外光谱、电喷雾电离质谱以及单晶X射线衍射分析（化合物1~4）完成了表征。对化合物1开展了图集分析。通过密度泛函理论计算估算了3a与3b的相对能量，结果显示二者的能量差值较小。