稀土金属硅胺基化合物晶体结构

DJ_Tokyo

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稀土金属硅胺基化合物晶体结构

如图1所示（由ChemBioDraw [1]绘制）为[RE{N(TMS)2}3] [2]（TMS= SiMe3; RE = Sc(CCDC [3]: 1519926–1519927[2a], 1255982[2b]), Y(CCDC:1305959 [2c]), Lu(CCDC: 666167 [2d]), Yb(CCDC171898 [2e], 2348421 [2f], 2339001 [2g]), Tm(CCDC:1814979 [2h]), Er(CCDC: 1302412 [2i]), Ho(CCDC:2109790 [2j]), Dy(CCDC: 1302411 [2i], 2109789 [2j],2339364 [2k]), Tb(CCDC: 220014 [2l], 2109788 [2j]), Gd(CCDC: 2109791[2l]), Eu(CCDC 1150705 [2b]), Sm(CCDC178900 [2m], 231202 [n]), Nd(CCDC1272652 [2o], 1272653 [2p]), Ce(CCDC1241289 [2q]), La(CCDC 2191891 [2r])）。

                              

▲图1 [RE{N(TMS)2}3]结构

如图2所示为[RE{N(SiHMe2)(tBu)}3][4]（RE = Sc(CCDC: 1542429[4a]), Y(CCDC: 1542430 [4a]), Lu(CCDC: 1542433[4a]), Er(CCDC: 1315802 [4b])）、[RE{N(SiHMe2)(dipp)}3][5]（RE = Sc(CCDC:1838231), Y(CCDC:1838233), Lu(CCDC: 1838230)）、[RE{N(SiMe3)(tBu)}3][6]（RE = Sm(CCDC:262003 [6a]), Ce(CCDC: 1032844 [6b])）、[La{N(SiMe3)(SiMe2tBu)}3][6]（CCDC:1032843）、[La{N(SiMe3)(dipp)}3][7]（CCDC:767402）和[La{N(SiMe2tBu)2}3][6]（CCDC:1032845）。

▲图2 [RE{N(R1)(R2)}3]结构

如图3所示为[{(dipp)(Me2HSi)N}2REN(SiMe2OR)(dipp)]（R = iPr, RE = Y(CCDC:2068523 [8]); R = CHPh2, RE = Y(CCDC:2068530 [8]), Lu(CCDC: 2068524 [8]); R =CH(Me)Ph, RE = Y(CCDC:1838232 [5]), Lu(CCDC 2068525 [8])）。

▲图3 [{(dipp)(Me2HSi)N}2REN(SiMe2OR)(dipp)]结构

如图4所示为[RE(κ2-N,O-Me3SiNC6H4-o-OR)3] [9]（R= Ph, RE = Y(CCDC:174207), Yb(CCDC: 174205–174206), Nd(CCDC: 174202), La(CCDC: 174198); R = Me, RE = Nd(CCDC:174200)）。

▲图4 [RE(κ2-N,O-Me3SiNC6H4-o-OR)3]结构

如图5所示为[Ce{κ2-N,F-N(TMS)(ofp)}3] [10]（CCDC:1500141; ofp = o-fluorophenyl）、[RE{κ2-N,F-N(TMS)(pfp)}3]（RE = Sm(CCDC:117064 [11a]), Ce(CCDC: 978666 [11b]);pfp = pentafluorophenyl）、[Sm{N(TMS)(pfp)}3(THF)] [12]（CCDC:150769; THF = tetrahydrofuran, CAS: 109-99-9）、[Ce{κ2-N,F-N(TMS)(pfp)}{N(TMS)(pfp)}2(κ2-O,O-18-C-6)]（CCDC978667 [11b]; 18-C-6 = 18-Crown-6, CAS: 17455-13-9, CCDC: 1178076 [13a], 1178077 [13b], 1178078 [13c], 1915344 [13d], 2304101[13e]）和[Ce{κ2-N,F-N(TMS)(pfp)}{N(TMS)(pfp)}2(κ2-N,N-dtbpy)]（CCDC978669 [11b]; dtbpy = 4,4'-di-tert-butyl-2,2'-bipyridine,CAS: 72914-19-3, CCDC: 744523 [14a], 1567116–1567118[14b], 2234384 [14c],2332091 [14d]）。

▲图5 氟代苯基硅胺基稀土金属化合物结构

如图6所示为[RE{κ2-N,N-N(R2)(C5H3N-R1)}3]（R1 = 4-Me, R2 = TMS, RE = Sc(CCDC 706703 [15a]);R1 = 6-Me, R2 = TMS, RE = Er(CCDC191405 [15b]), Gd(CCDC 191404 [15b]); R1 = 6-Me, R2 = SiMe2tBu, RE= Nd(CCDC211074 [15c]), Ce(CCDC 211073 [15c])）和[Y{κ2-N,N-N(TMS)(C5H3N-Me-6)}2{HN(TMS)(C5H3N-Me-6)}]（CCDC1228902 [15d]）。

▲图6 吡啶基硅胺基稀土金属化合物结构

如图7所示为[Y{N(SiHMe2)(tBu)}3(DEE)][4a]（CCDC:1542431; DEE = diethyl ether, CAS: 60-29-7）、[RE{N(SiHMe2)(tBu)}3(THF)][4a]（RE = Y(CCDC:1542432), Lu(CCDC: 1542434)）、[RE{N(SiHMe2)(dmp)}3(THF)] [8]（RE = Y(CCDC:2068527), Lu(CCDC:2068528); dmp = 2,6-dimethylphenyl）、[Y{N(SiHMe2)(dipp)}3(Py)] [8]（CCDC:2068522; Py = pyridine, CAS: 110-86-1）、[RE{N(SiHMe2)2}3(1,10-Phen)][16]（RE = Sc(CCDC:674051), Nd(CCDC: 674050); 1,10-Phen = 1,10-Phenanthroline, CAS: 66-71-7,CCDC: 1226133 [17a], 2041415[17b]）、[Sc{N(SiHMe2)2}3(THF)][18]（CCDC1239262）、[Y{N(TMS)2}3(THF)] [19]（CCDC2056064）、[RE{N(TMS)2}3(O=CPh2)]（RE = Tb(CCDC:1227115 [20a]), Pr(CCDC: 903010 [20b]),Ce(CCDC: 903009[20b]), La(CCDC: 2196153 [20c])）、[RE{N(TMS)2}3(9-Fluorenone)]（RE = Pr(CCDC903012 [20b]), Ce(CCDC 903011 [20b]);9-Fluorenone, CAS: 486-25-9, CCDC: 1157855 [21a], 1513109 [21b], 1903499 [21c], 2049630 [21d], 2259718 [21e]）、[RE{N(TMS)2}3(TPO)]（RE = Eu(CCDC:1944305 [22a]), La(CCDC 1214429 [22b], 893258[22c]); TPO = Triphenylphosphine oxide, CAS: 791-28-6, CCDC:1275215 [23a], 1275216 [23b], 1275217 [23c], 1275218–1275221 [23d], 1275222 [23e], 1275223 [23f], 1275224 [23g], 186887 [23h], 186888 [23i], 638294 [23j], 653016 [23k], 1417082 [23l], 1487429 [23m], 1562959 [23n], 2016065 [23o], 2065420 [23p], 2069720 [23q], 2025561 [23r], 2113696 [23s], 2033355 [23t], 2075134 [23u], 2033356 [23t], 2043631 [23v], 2076602 [23w], 2106549 [23x], 2337091 [23y], 2337092 [23z], 2360267 [23aa], 2266007[23ab], 2408995[23ac], 2431088[23ad], 2476365[23ae]）、[RE{N(TMS)(Ph)}3(THF)]（RE = Sc(CCDC: 1858320 [24a]), Y(CCDC:1858316 [24a]), Lu(CCDC:1858321 [24a]), Yb(CCDC:2216480 [24b]), Ho(CCDC:1858323 [24a]), Dy(CCDC:1858322 [24a], 2216479 [24b]), Tb(CCDC:1858324 [24a]), Gd(CCDC:1858318 [24a]), Nd(CCDC: 1304674 [24c]), Pr(CCDC:1858326 [24a]), Ce(CCDC:1858319 [24a]), La(CCDC:1858327 [24a])）、[RE{N(TMS)(Cy)}3(THF)]（RE = Y(CCDC:1858317 [24a]), Ho(CCDC: 1858325 [24a])）和[RE{N(SiHMe2)2}2{N(TMS)(dipp)}(THF)]（RE = Y(CCDC: 1440811[25a]), Lu(CCDC: 1430243 [25b])）。

▲图7 四配位不对称硅胺基稀土金属化合物

如图8所示为[{(Me3Si)2N}3RE(μ-Cl)Li(THF)3]（RE = Y(CCDC: 1051282[26a], 1305958 [2c],2337045 [26b]), Yb(CCDC: 173988 [26c]),Er(CCDC: 1817193[26a], 1039489[26d]), Dy(CCDC: 1039488 [26d]),Eu(CCDC: 187382[26e]), Sm(CCDC: 187383 [26e]),Nd(CCDC: 1174298 [26f]),Pr(CCDC: 221101 [26g]),La(CCDC: 1536206[26h])）。

▲图8 [{(Me3Si)2N}3RE(μ-Cl)Li(THF)3]结构

如图9所示为[{(CH2SiMe2)2N}3RE(μ-Cl)Li(L1)3(L2)][27]（L1= L2 = DEE, RE = Yb(CCDC: 162894), Tm(CCDC: 162893), Er(CCDC: 162892), Ho(CCDC: 162891), Dy(CCDC: 162890), Tb(CCDC: 162889); L1 = THF, L2 = DEE, RE = Gd(CCDC: 162888), Sm(CCDC: 162886); L1 = L2 = THF, RE = Eu(CCDC: 162887)）。

▲图9 [{(CH2SiMe2)2N}3RE(μ-Cl)Li(L1)3(L2)]结构

如图10所示为一些四价铈硅胺基化合物[{(TMS)2N}3CeIVX]（X = F(CCDC: 951415 [28a]),Cl(CCDC:162978 [28bc]), Br(CCDC 231596 [28c]),I(CCDC: 1011851 [28d]), NCS(CCDC1011853 [28d]), OTMS(CCDC: 1057502 [28e])）、[{(TMS)2N}3CeIVN3]n[28d]（CCDC: 1011852）、[{(TMS)2N}3CeIV(μ-η2:η2-O2)CeIV{N(TMS)2}3] [28f]（CCDC:774599–774600）、[{(TMS)2N}3CeIVCl(N≡CPMP)] [28g]（CCDC829659; PMP = p-methoxy‌phenyl）、[{(TMS)2N}3CeIV=O][Li(crypt)] [28h]（CCDC:1569782; crypt = 4,7,13,16,21-Pentaoxa-1,10-diazabicyclo[8.8.5]tricosane, CAS: 31364-42-8,CCDC: 1177453 [29a], 1177453 [29b], 2376748 [29c]）、[{(TMS)2N}3CeIV(κ2-O,O-NO3)][Li(crypt)] [28h]（CCDC:1569781）、[CeIV{N(SiHMe2)2}4][28i]（CCDC:904595）、[{Me2Si(Me2HSiNSiMe2)2N}3CeIVCl] [28j]（CCDC:2123365）和[{(TMS)2N}3CeIV(μ3-O)M]2 [28f]（M = Na(CCDC774596), K(CCDC774597)）。

▲图10 四价铈硅胺基化合物结构

如图11所示为[{Me2Si(Me2HSiNSiMe2)2N}3Ce(THF)] [28j]（CCDC:2123368）。

▲图11 [{Me2Si(Me2HSiNSiMe2)2N}3Ce(THF)]

如图12所示为[{(TMS)2N}3RER][X]（R = Cl, X = Li(THF)4, RE = Er(CCDC: 1051281[26a]), Sm(CCDC: 216287 [30a]);R = Cl, X = NEt4, RE = Ce(CCDC: 1481443 [30b]);R = O(CH2)2OMe, X = K(crypt), RE = Y(CCDC: 2215326[30c]); R = OnPr, X = (Oxetane)K(18-C-6), RE = Er(CCDC: 2215335[30c]), Ho(CCDC: 2215330 [30c]),Oxetane, CAS: 503-30-0; R = OnBu, X = K(crypt), RE = Y(CCDC: 2215329[30c]); R = OTMS, X = Na(12-C-4)2, RE = Yb(CCDC: 114230 [30d]),Sm(CCDC: 114229 [30d]),12-C-4 = 12-Crown-4, CAS: 294-93-9, CCDC: 1274767[31]; R = OTMS, X = Li(THF)4, RE = Nd(CCDC: 1174299[26f]); R = OTMS, X = Li(crypt), RE = Ce(CCDC: 1569784 [28h]); R = Ph, X = K(18-C-6)2, RE = Gd(CCDC: 2098003[30e]); R = BiPh2, X = K(crypt), RE = Gd(CCDC: 2098002[30e], 2098004 [30e]); R = Bn, X = K(THF), RE = Y(CCDC: 1547058[30f]); R = Bn, X = Li(tmeda)2, RE = Nd(CCDC: 1568982[30g]), tmeda = N,N,N',N'-Tetramethylethylenediamine,CAS: 110-18-9; R = TEMPO, X = K(18-C-6), RE = Gd(CCDC: 2097999[30e]), TEMPO = 2,2,6,6-Tetramethyl-1-piperinedinyloxy, CAS: 2564-83-2,CCDC: 1272626 [32a], 1272627 [32b], 1272628 [32c], 1272629 [32d], 1272630 [32e], 651858 [32f], 737221 [32g]; R = TEMPO, X = (THF)K(crypt), RE = Gd(CCDC: 2097997[30e]); R = N(TMS)2, X = K(THF)5, RE = Gd(CCDC: 1998650 [30h]),Pr(CCDC: 242608 [30i]),La(CCDC: 242607 [30i]);R = N(TMS)2, X = (DEE)Na(THF)4,RE = Ce(CCDC: 242739 [30i])）、[{(TMS)2N}3SmC≡CPhNa(THF)3] [30d]（CCDC:114231）、[{(TMS)2N}3Y(μ-H)K(18-C-6)][30a]（CCDC:2215334）、[{(TMS)2N}2Ce{μ-N(TMS)2}2Li(THF)][30j]（CCDC:973029）、[{(TMS)(dep)N}3YCl][Li(THF)4][30k]（CCDC:684088, dep = 2,6-diethylphenyl）、[RE{N(SiHMe2)2}4][X]（X = Li(THF)4, RE = Yb(CCDC: 2348425[2f]), Ce(CCDC: 1954724 [30l]);X = Li(Py)4, RE = Ce(CCDC: 1954721 [30l]);X = (THF)Li(12-C-4), RE = Ce(CCDC: 1954722 [30l]);X = Li(tmeda)2, RE = Ce(CCDC: 1954723 [30l]);X = Na, RE = Eu(CCDC: 1018198[30m]); X = K, RE = Eu(CCDC: 1018199 [30m]),Ce(CCDC: 1000019[30n])）、[{(TMS)2N}3EuIICl][{(THF)5EuII(μ-Cl)}2] [2h]（CCDC:1814974）和[(μ-OCH2CH2O){Lu(N(TMS)2)3}2][30a]（CCDC:2215328）。

▲图12 四配位稀土金属硅胺基化合物结构

如图13所示为[{κ2-C,N-(TMS)NSiMe2CH2}RE{N(TMS)2}2][X]（X = Na(THF)3, RE = Yb(CCDC: 127777[33a]); X = K(tol), RE = Y(CCDC: 1921473[30f]); X = K(crypt), RE = Y(CCDC: 2215332 [30c]),Er(CCDC: 2215337 [30c]),Ho(CCDC: 2215336 [30c]);X = K(18-C-6), RE = Y(CCDC: 2215333 [30c])）、[{κ2-C,N-(TMS)NSiMe2CH2M}RE{N(TMS)2}2]（M = Li(tmeda), RE = Y(CCDC: 614771 [33b]);M = K, RE = Yb(CCDC: 614770 [33b])）、[(THF){(TMS)(Ph)N}Yb(μ2-η1:η1-N(TMS)(Ph))]2（CCDC: 171222[33c]）、[{(Me2RSi)2N}2RE{μ2-η1:η1-N(SiRMe2)2}]2（R = H, RE = Y(CCDC: 601446 [33d]),La(CCDC: 679487 [33e]);R = Me, RE = Yb(CCDC: 2039521[33f], 2032027 [33g])）、[(THF){(Me2HSi)2N}REII{μ2-η1:η1-N(SiHMe2)2}2REII{μ2-η1:η1-N(SiHMe2)2}2REII{N(SiHMe2)2}(THF)]（RE = Yb(CCDC: 139829 [33h]),Eu(CCDC: 1018197 [30m]),Sm(CCDC: 118713 [33i])）、[{(TMS)2N}Y{μ2-η1:η1-N(TMS)2}(μ3-H)K]2[30f]（CCDC: 1571534）、[{(Me2HSi)2N}2Y{{μ2-η1:η1-N(SiHMe2)2Li}]2[16]（CCDC: 674052）、[{(Me2HSi)2N}3EuII{μ-N(SiHMe2)2}EuII]2[30m]（CCDC: 1018200）和[{(TMS)2N}3CeIV(μ2-O)CeIV{N(TMS)2}{μ2-η1:η1-N(TMS)2}(μ3-O)K]2 [28f]（CCDC:774598）。

▲图13 四元环稀土金属硅胺基化合物结构

如图14为[RE{NR(SiHMe2)}3(THF)2]（R = Ph, RE = Sc(CCDC: 2068531[8]),Y(CCDC: 2068529[8]),Lu(CCDC: 2068526[8]);R = SiHMe2, RE = Y(CCDC: 1302414[2i]), Lu(CCDC: 1239260 [18]),Yb(CCDC: 801549[34a], 2348422[2f]), Ho(CCDC: 624685 [34b]),Gd(CCDC: 867418[34c]), Eu(CCDC: 1018196 [30m]),Sm(CCDC: 146252[34d]), Nd(CCDC: 1302415 [2i]), Pr(CCDC: 928292 [34e]),Ce(CCDC: 928291 [34e]),La(CCDC: 1239261[18])）、[RE{N(TMS)2}3(N≡CR)2]（R = Ph, RE = Y(CCDC: 1305961[2c]); R = TMS, RE = Yb(CCDC: 2144894[34f]); R = Cy, RE = Er(CCDC: 619243 [34g]),Nd(CCDC: 178208 [34h])）、[RE{κ2-N,N-Me2N(CH2)2N(TMS)}3]（RE = Lu(CCDC: 1222217 [34i]),Er(CCDC: 1222213 [34i]),Eu(CCDC: 1222214 [34i])）和[{(pfp)(TMS)N}2Ce{κ2-N,F-N(TMS)(pfp)}2][{(pfp)(TMS)N}2Ce (18-C-6)] [11b]（CCDC: 978668）。

▲图14 五配位和六配位稀土金属硅胺基化合物结构

如图15为[REII{N(TMS)(SiRMe2)}3]（R = Me, X = Li, RE = Yb(CCDC: 614772[33b]); R = Me, X = Na, RE = Yb(CCDC: 1126696 [35a]),Eu(CCDC: 1126695 [35a]);R = Me, X = K, RE = Yb(CCDC: 1296135 [33b]),Sm(CCDC: 1253434 [35b]);R = Me, X = K(DME)3, RE = Yb(CCDC: 1574630 [35c]);R = Me, X = K(18-C-6)2, RE = Y(CCDC: 1950293 [35d]),Tm(CCDC: 1950294 [35d]),Er(CCDC: 1950290 [35d]),Ho(CCDC: 1950298 [35d]),Dy(CCDC: 1950289 [35d]),Tb(CCDC: 1950291 [35d]),Gd(CCDC: 1950296 [35d]);R = Me, X = K(crypt), RE = Dy(CCDC: 1567580 [35e]),Tb(CCDC: 1567581 [35e]),Gd(CCDC: 1567585 [35e], 1950299 [35d]); R = Me, X = Rb(crypt), RE = Tm(CCDC: 1567584 [35e]),Er(CCDC: 1567586 [35e]),Ho(CCDC: 1567582 [35e]),Nd(CCDC: 1567583 [35e]);R = tBu, X = K(DME)3, RE = Sm(CCDC: 1534379 [35f]);R = tBu, X = K(tol)2, RE = Eu(CCDC: 1534381 [35f]),Sm(CCDC: 1534380[35f]); R = tBu, X = K(crypt), RE = Yb(CCDC: 1534378 [35f]),Tm(CCDC: 1534377 [35f]),Eu(CCDC: 1534376 [35f]),Sm(CCDC: 1534375 [35f])）。

▲图15 三配位二价稀土金属硅胺基化合物结构

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