稀土金属硅烷基化合物晶体结构

DJ_Tokyo

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稀土金属硅烷基化合物晶体结构

如图1所示（由ChemBioDraw [1]绘制）为[RE(CH2SiMe2R)3(THF)2] [2]（R= Me, RE = Sc(CCDC: 1473387 [2a]), Y(CCDC: 1909166 [2b]), Lu(CCDC: 184759 [2c]), Yb(CCDC: 177172 [2d], 184758 [2c]), Tm(CCDC: 1909164 [2b]), Er(CCDC: 184757 [2c], 1909167 [2b]), Ho(CCDC: 1909169 [2b]), Dy(CCDC: 1909165 [2b]), Tb(CCDC: 1909168 [2b]); R = Ph, RE = Sc(CCDC: 195362 [2e]); THF = tetrahydrofuran,CAS: 109-99-9, CCDC: 1116822–1116823 [3a], 1116824–1116825 [3b]）。

                              

▲图1 [RE(CH2SiMe2R)3(THF)2]结构

如图2所示为[Lu(CH2TMS)3(Py)2][4]（CCDC:1577359; TMS = SiMe3; Py = pyridine, CAS: 110-86-1,CCDC: 1240728 [5a], 1240729 [5b], 69595–695959 [5c], 759557 [5d], 1966460–1966461 [5e]）、[RE(CH2TMS)3(DMAP)2][6]（RE = Y(CCDC: 2111017 [6a]), Lu(CCDC: 1429585 [6b]), Yb(CCDC: 1574066 [6c], 2432646 [6d]); DMAP = 4-N,N-dimethylaminopyridine,CAS: 1122-58-3, CCDC: 1116498–1116499 [7a], 1116500 [7b], 801515 [7c], 1981857 [7d], 1981889–1981890 [7d], 2100938 [7e], 2174547 [7f], 2338083 [7g], 2381187 [7h], 2458381 [7i], 2475260 [7j]）、[Ho(CH2TMS)3(3,5-Lut)2] [2b]（CCDC:1950993; 3,5-Lut = 3,5-lutidine, CAS: 591-22-0, CCDC: 180526 [8]）、[Ho(CH2TMS)3(Quin)2][2b]（CCDC:1950992; Quin = quinuclidine, CAS: 100-76-5, CCDC: 1245612 [9a], 1245613–1245614 [9b], 1245615 [9c]）、[Ho(CH2TMS)3(O=PCy3)2] [2b]（CCDC:1950994; O=PCy3 = tricyclohexylphosphineoxide, CAS: 13689-19-5, CCDC: 1197861 [10a], 2043630 [10b]）、[(κ2-N,N-tmeda)RE(CH2TMS)3(THF)3]（RE = Sc(CCDC: 2351144 [11]), Y(CCDC: 2111016 [6a]), Lu(CCDC: 2351150 [11]), Sm(CCDC: 2369795 [11]); tmeda = N,N,N',N'-Tetramethylethylenediamine,CAS: 110-18-9, CCDC: 2123810 [12]）和[(κ2-N,N-dtbpy)Lu(CH2TMS)3][13]（CCDC: 690301; dtbpy = 4,4'-di-tert-butyl-2,2'-bipyridine,CAS: 72914-19-3, CCDC: 744523 [14a], 1567116–1567118[14b], 2234384 [14c],2332091 [14d]）。

▲图2 [RE(CH2TMS)3(L)2]结构

如图3所示为[RE(CH2TMS)3(THF)3]（RE = Y(CCDC: 1101559 [15]), Sm(CCDC: 184756 [2c])）、[RE(CH2TMS)3(OBCH)3] [16]（RE= Lu(CCDC: 2487190 [16a]), Yb(CCDC: 2487191 [16b]), Er(CCDC: 2487192 [16c]); OBCH = 7-oxabicyclo[4.1.0]heptane, CAS:286-20-4, CCDC: 284531 [17], 1256934 [17]）、[(κ3-O,O,O-diglyme)RE(CH2TMS)3] [11]（RE = Sc(CCDC: 2351145), Y(CCDC: 2351147), Lu(CCDC: 2351146); diglyme = 2-methoxyethylether, CAS: 111-96-6）、[(κ2-O,O-diglyme)Lu(CH2TMS)3(THF)][18]（CCDC:245414）、[(κ3-O,O,O-triglyme)Lu(CH2TMS)3] [11]（CCDC: 2351143, triglyme = 2,5,8,11-tetraoxadodecane,CAS: 112-49-2）、[(κ4-O,O,O,O-triglyme)Y(CH2TMS)3] [11]（CCDC: 2351142）、[(κ3-O,N,O-L)Sc(CH2TMS)3] [19]（CCDC:601302; L = bis(2-methoxyethyl)(trimethylsilyl)amine/Me3SiN(CH2CH2OMe)2）和[(κ2-P,P-dmpe)RE(CH2TMS)3(THF)]（RE = Sc(CCDC: 2351149 [11]), Y(CCDC: 2111014 [6a]), Lu(CCDC: 2351148 [11]); dmpe = 1,2-bis(dimethylphosphanyl)ethane,CAS: 23936-60-9, CCDC 1220933 [20]）。

▲图3 醚和膦配体支撑稀土金属硅烷基化合物

如图4所示为[(κ3-O,O,O-12-C-4)Sc(CH2TMS)3] [21]（CCDC:284856; 12-C-4 = 12-Crown-4, CAS: 294-93-9, CCDC: 1274767 [22]）、[(κ4-O,O,O,O-12-C-4)RE(CH2TMS)3] [23]（RE = Y(CCDC: 211480), Lu(CCDC: 211481)）、[(κ3-N,N,N-Me3[9]aneN3)RE(CH2TMS)3] [24]（RE = Sc(CCDC: 276569 [24a], Y(CCDC: 298703 [24b]); Me3[9]aneN3 = 1,3,5-trimethyltriazacyclohexane）、[(κ3-S,S,S-[9]aneS3)Sc(CH2TMS)3] [25]（CCDC:267474 [25a], 267474 [25b]; [9]aneS3 = 1,4,7-trithiacyclonane, CAS: 6573-11-1, CCDC1270437 [26]）、[(κ3-N,N,N-L)Sc(CH2TMS)3] [27]（CCDC:606108; L = N,N,1,4,6-pentamethyl-1,4-diazepan-6-amine）和[(κ3-N,N,N-L)RE(CH2TMS)3] [28]（RE = Sc(CCDC: 709827), Y(CCDC: 709828); L = 1,4,6-trimethyl-6-pyrrolidin-1-yl-1,4-diazepane）。

▲图4 环状配体支撑稀土金属硅烷基化合物

如图5所示为[RE(CH2TMS)3(IMes)] [29]（RE = Sc(CCDC: 2052320 [29a]), Lu(CCDC: 763326 [29b]); Imes = 1,3-bis(1,3,5-trimethylphenyl)imidazole-2-ylidene,CCDC: 1190205 [30]）、[Sc(CH2TMS)3(IDmp)][31]（CCDC:830612; IDmp = 1,3-bis(2,6-dimethylphenyl)imidazole-2-ylidene）、[RE(CH2TMS)3(IDipp)]（RE = Sc(CCDC: 830613 [31]), Y(CCDC: 763325 [29b]); IDipp= 1,3-bis(2,6-diisopropylphenyl)imidazole-2-ylidene; CCDC: 133745 [32a], 2442978 [32b]）、[RE(CH2TMS)3(Me2IiPr)(THF)] [33]（RE = Lu(CCDC: 632997), Er(CCDC: 632996); Me2IiPr = 1,3-di-iso-propyl-4,5-dimethylimidazol-2-ylidene,CCDC: 859118 [34]）、[RE(CH2TMS)3(Me2IiPr)2] [33]（RE = Lu(CCDC: 632998), Er(CCDC: 1258535)）和[(RCAAC)RE(CH2TMS)3] [35]（R= Me, RE = Sc(CCDC: 2183254), Y(CCDC: 2183256), Lu(CCDC: 2183258); R =Et, RE = Sc(CCDC: 2183255), Y(CCDC: 2183256), Lu(CCDC: 2183259); CAAC= cyclic (alkyl)(amino)carbene, MeCAAC = 1-(2,6-diisopropylphenyl)-2,2,4,4-tetramethyl-3,4-dihydro-2H-pyrrol-1-ium-5-ide,CCDC: 1472173 [36]; EtCAAC = 1-(2,6-diisopropylphenyl)-4,4-diethyl-2,2-dimethyl-3,4-dihydro-2H-pyrrol-1-ium-5-ide）。

▲图5 氮杂卡宾配体支撑稀土金属硅烷基化合物

如图6所示为[CpPhnPrRE(CH2TMS)3][Li(THF)3(DEE)][37]（RE = Y(CCDC: 886169), Lu(CCDC: 886167), Tm(CCDC: 886168), Er(CCDC: 886165), Ho(CCDC: 886166); CpPhnPr = 1-phenyl-2,3,4,5-tetrapropylcyclopentadienyl;DEE = diethyl ether, CAS: 60-29-7, CCDC: 1139373 [38a], 2282461–2282469 [38b]）。

▲图6 [CpnPrRE(CH2TMS)3][Li(THF)3(DEE)]结构

如图7所示为[Li{(TMSCH2)2Sc(μ-CH2TMS)2}2][Li(THF)4] [39]（CCDC:2215407）、[(TMSCH2)Y(μ2-CH2TMS)2(μ3-CH2TMS)3Li3] [39]（CCDC:2215408）、[La(CH2TMS)4(THF)][Li(THF)4] [39]（CCDC:2215409）和[(TMSCH2)Y(μ3-OtBu)4(μ4-Cl){Li(THF)}4][Y(CH2TMS)4] [40]（CCDC:1311700）。

▲图7 锂-稀土金属硅烷基化合物结构

早在1980年，Vollershtein, E. L.等人 [41]报道了三氯化钕（NdCl3, Neodymium(III) chloride, CAS: 10024-93-8）与等当量三(三甲基硅基亚甲基)锂[42]（LiCH2TMS,(Trimethylsilyl)methyllithium, for [Li(μ3-CH2TMS)]6,CAS: 110558-46-8, CCDC: 1181797 [42a], 1960466 [42b], CCDC: 2490906）在室温下的反应，并声称得到二聚体结构，但并未得到晶体结构。笔者也尝试过NdCl3与三当量LiCH2TMS的反应，以正己烷 [43]（C6H14, n-hexane,CAS: 110-54-3, CCDC: 103189）作溶剂，于零下35摄氏度静置，成功培养得到了蓝色晶体，如图8左所示，并且成功将其封在充满氩气的毛细管中，如图8右所示，但在常温下，充满氩气毛细管中的蓝色晶体很快变成无色（大约十几分钟），并且没有X射线衍射信号，也尝试了低温测试，但衍射信号不好，因此遗憾地未能确定其结构，读者朋友如有条件，可尝试确定其结构。

▲图8 三氯化钕与三当量三(三甲基硅基亚甲基)锂反应产物晶体

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