含8—羟基喹啉类配体的新型钛配合物[O,N]CpTiCl2的合成及其催化乙烯聚合研究

茂金属催化烯烃聚合的活性中心被认为是14电子结构的金属阳离子配合物[Cp2MR] +(R为烷基 ),并且金属中心的Lewis酸性和周围茂配体的空间构型对其催化活性及聚合产物的结构有直接的影响[1,2].然而,茂金属须大量MAO存在下才能显示高活性,并且其稳定性较差,这都一定程度上限制了茂金属催化剂的实际应用.近几年来,将含非环戊二烯基配体的金属配合物应用于烯烃均相聚合的研究大量出现[3],其中非环戊二烯基配体有含氮化合物 [4～9]和含氧化合物[10～15]等,这些非茂配合物可催化乙烯或丙烯聚合,但活性一般较低 .     

含8-羟基喹啉类配体的新型钛配合物[O,N]CpTiCl2的合成及其催化乙烯聚合研究

茂金属催化烯烃聚合的活性中心被认为是14电子结构的金属阳离子配合物[Cp2MR] +(R为烷基 ),并且金属中心的Lewis酸性和周围茂配体的空间构型对其催化活性及聚合产物的结构有直接的影响[1,2].然而,茂金属须大量MAO存在下才能显示高活性,并且其稳定性较差,这都一定程度上限制了茂金属催化剂的实际应用.近几年来,将含非环戊二烯基配体的金属配合物应用于烯烃均相聚合的研究大量出现[3],其中非环戊二烯基配体有含氮化合物 [4～9]和含氧化合物[10～15]等,这些非茂配合物可催化乙烯或丙烯聚合,但活性一般较低 .     

含8-羟基喹啉类配体的新型钛配合物[O,N]CpTiCl_2的合成及其催化乙烯聚合研究

茂金属催化烯烃聚合的活性中心被认为是1 4电子结构的金属阳离子配合物 [Ｃｐ2 ＭＲ]+ (Ｒ为烷基 ) ,并且金属中心的Ｌｅｗｉｓ酸性和周围茂配体的空间构型对其催化活性及聚合产物的结构有直接的影响[1,2 ] .然而 ,茂金属须大量ＭＡＯ存在下才能显示高活性 ,并且其稳定性较差 ,这都一定程度上限制了茂金属催化剂的实际应用 .近几年来 ,将含非环戊二烯基配体的金属配合物应用于烯烃均相聚合的研究大量出现[3] ,其中非环戊二烯基配体有含氮化合物[4～ 9] 和含氧化合物[10～ 15] 等 ,这些非茂配合物可催化乙烯或丙烯聚合 ,但活性一般较低 .茂金…     

原位反应法制备CpTi(dbm)Cl2/MgCl2载体型催化剂及其催化乙烯聚合的研究

非茂催化剂对烯烃聚合显示出优异的催化特性,是继ziegler—Natta催化剂及茂金属催化剂之后的新一代烯烃聚合催化剂^[1],其中非环戊二烯基配体有含氮化合物[2-8]和含氧化合物^[9-15]等,这些非茂配合物可催化乙烯或丙烯聚合．将金属中心与一个环戊二烯基和一个非环戊二烯基配体而     

桥联茂钛配合物催化丙烯聚合反应选择性的理论研究

采用密度泛函方法对3种不同类型的硅桥联茂钛配合物[Me_2SiN(Me_4Cp)TiCl_2(A),Me_2SiCpFluTiCl_2(B)及Me_2SiInd_2TiCl_2(C)]催化丙烯聚合反应的选择性进行了理论研究.计算结果表明,硅桥联茂金属配体的空间结构是其催化烯烃聚合反应的区域选择性和立体选择性的主要原因.聚合过程中,α-烯烃配位有1,2插入(一级插入)和2,1插入(二级插入)2种方式,3种硅桥联茂金属催化剂均表现为烯烃的一级插入,这种区域选择性与催化剂硅桥联配体的刚性结构密切相关.对烯烃聚合反应链增长机理进行了理论计算,结果表明,具有Cs对称性的Me_2SiN(Me_4Cp)TiCl_2和Me_2SiCpFluTiCl_2催化丙烯聚合分别得到无规立构和间规立构的聚烯烃产物,而具有C_2对称性的Me_2SiInd_2TiCl_2催化丙烯聚合得到等规立构的聚烯烃产物,与实验结果一致.     

氮配位单茂金属烯烃聚合催化剂

本文综述了近些年来以含氮基团为阴离子配体的单茂金属化合物作为烯烃精确聚合的催化剂的研究。氮配位单茂金属催化剂在烯烃聚合中显示出独特的特性,特别是对于乙烯的共聚合,不仅能得到Ziegler-Natta催化剂和传统茂金属催化剂不能合成的新的共聚物,还有优于其他单茂金属催化剂的共聚活性。环戊二烯基和含氮阴离子配体的改性是所得催化剂聚合效果的关键。本文涉及了乙烯均聚以及乙烯与α-烯烃(己烯-1、辛烯-1等)、苯乙烯和环烯烃(降冰片烯、四环十二碳烯等)的共聚合。     

双组分茂金属催化剂催化乙烯聚合的研究

选择能形成支链的不对称桥联茂金属化合物Me2 C[(Cp) (Ind) ]ZrCl2 和非桥联的不同结构的茂金属化合物二氯二 (烯基取代环戊二烯 )锆如 ( Cp) 2 ZrCl2 ,(Cp) 2 ZrCl2 和 (Cp) 2 ZrCl2 ,以MAO为助催化剂 ,分别组成三组双组分茂金属催化剂的催化体系 ,催化乙烯聚合 .结果表明 ,两类催化剂组成的双组分茂金属催化体系催化乙烯聚合能得到支化的宽分子量分布的聚乙烯 ;聚合温度和改变两种茂金属催化剂的摩尔比对催化活性和分子量有很大影响 .因此可以利用改变双组分茂金属催化剂的摩尔比例和聚合温度来调控聚合物的分子量和分子量分布 .改变两种茂金属催化剂的摩尔比和聚合温度也能使聚合物的结晶度发生改变     

茂金属聚合催化剂的研究现状

198 0年德国汉堡大学的化学家 Sinn等[1] 发现了烯烃聚合用的茂金属催化剂 .茂金属催化剂为两个环戊二烯中间夹有过渡金属如 Zr、Hf、Ti等的具有三明治结构的有机金属化合物 .茂金属催化剂与传统的多相 Ziegler- Natta催化剂相比 ,具有可溶且聚合活性物种单一 ,对乙烯等烯烃的聚合活性高 ,高分子产物的分子量及组成分布窄等特点 .选择不同的茂金属催化剂 ,可获得所需立构规整性的高分子物 ,除能获得全同立构的聚烯烃外 ,还可获得由 Ziegler- Natta催化剂不能合成的间规立构聚烯烃 ,如聚苯乙烯 [2 ]与聚丙烯 [3 ] .由 Ziegler- Natta催化…     

稀土金属有机配合物化学60年

60年来稀土金属有机配合物化学取得重要发展. 辅助配体从环戊二烯基,五甲基环戊二烯基,茚基发展到各种非茂配体,如双酚,β-二亚胺,胍基,脒基等. 配合物的种类从简单的三茂稀土配合物发展到各种形式的二茂稀土配合物和单茂稀土配合物. 非茂配体的应用不仅拓展了稀土金属有机配合物的结构种类,还极大推动稀土金属有机配合物在高分子和有机合成中的应用. 稀土金属有机配合物可有效催化烯烃均聚与共聚,共轭双烯烃以及极性单体的选择性聚合. 稀土金属有机配合物还能催化氢化,氢胺化和膦氢化等重要有机反应. 本文对稀土金属有机配合物化学过去60年的发展进行综述.     

含茂、非茂混合配体钛族络合物的合成与催化烯烃聚合的研究进展

目前金属有机钛族络合物的发展呈现出多元化的趋势:茂络合物、非茂络合物以及茂非茂混合配体络合物,而其中茂、非茂混合配体络合物是近年来发展的一个新亮点.关于茂钛族络合物、非茂钛族络合物近年已经有过许多的综述,而关于茂、非茂混合配体钛族络合物的综述却很少.综述了近年来茂、非茂混合配体钛族络合物合成与催化烯烃聚合的研究进展.     

芳二酚-茂型钛配合物[O,O]CpTiCl的合成及其催化乙烯聚合性能研究

制备了含二元芳香酚类配体 [O ,O]的茂型钛配合物 [O ,O]CpTiCl,并通过元素分析、IR、1 H NMR表征了其组成与结构 .结果表明 ,二元芳香酚类配体中两个O原子同时与金属中心原子Ti相连 ,形成环状结构 .研究表明 ,茂型钛配合物 [O ,O]CpTiCl在助催化剂甲基铝氧烷 (MAO)作用下 ,于 30℃、1 0 1× 10 5 Pa乙烯压力下即可催化乙烯聚合 ,并显示较高的活性 ,远高于未引入配体 [O ,O]的CpTiCl3的活性 ,并且 [O ,O]CpTiCl的催化活性依非茂酚类配体中芳香环的增大而下降 (C6 H4O2 ) >(C1 2 H8O2 ) >(C2 0 H1 2 O2 ) .此外 ,[O ,O]CpTiCl MAO体系催化活性随铝 钛比的增加呈上升而后衰减型 ,当铝 钛比为 5 0 0到 30 0 0之间时活性最高 ,所得聚乙烯具有双峰分布特征 ,其重均分子量Mw =12 5× 10 4,分子量分布为Mw Mn =7 4     

Formation of soluble hexanuclear neptunium(IV) nanoclusters in aqueous solution: growth termination of actinide(IV) hydrous oxides by carboxylates

Complexation of Np(IV) with several carboxylates (RCOO(-); R = H, CH(3), or CHR'NH(2); R' = H, CH(3), or CH(2)SH) in moderately acidic aqueous solutions was studied by using UV-vis-NIR and X-ray absorption spectroscopy. As the pH increased, all investigated carboxylates initiated formation of water-soluble hexanuclear complexes, Np(6)(μ-RCOO)(12)(μ(3)-O)(4)(μ(3)-OH)(4), in which the neighboring Np atoms are connected by RCOO(-)syn-syn bridges and the triangular faces of the Np(6) octahedron are capped with μ(3)-O(2-)/μ(3)-OH(-). The structure information of Np(6)(μ-RCOO)(12)(μ(3)-O)(4)(μ(3)-OH)(4) in aqueous solution was extracted from the extended X-ray absorption fine structure data: Np-O(2-) = 2.22-2.23 ? (coordination number N = 1.9-2.2), Np-O(RCOO(-)) and Np-OH(-) = 2.42-2.43 ? (N = 5.6-6.7 in total), Np···C(RCOO(-)) = 3.43 ? (N = 3.3-3.9), Np···Np(neighbor) = 3.80-3.82 ? (N = 3.6-4.0), and Np···Np(terminal) = 5.39-5.41 ? (N = 1.0-1.2). For the simpler carboxylates, the gross stability constants of Np(6)(μ-RCOO)(12)(μ(3)-O)(4)(μ(3)-OH)(4) and related monomers, Np(RCOO)(OH)(2)(+), were determined from the UV-vis-NIR titration data: when R = H, log β(6,12,-12) = 42.7 ± 1.2 and log β(1,1,-2) = 2.51 ± 0.05 at I = 0.62 M and 295 K; when R = CH(3), log β(6,12,-12) = 52.0 ± 0.7 and log β(1,1,-2) = 3.86 ± 0.03 at I = 0.66 M and 295 K.     

Synthesis, structural characterization, and theoretical investigation of compounds containing an Al-O-M-O-Al (M=Ti, Zr) core

We report a facile route to the first molecular compounds with the Al-O-M-O-Al (M=Ti, Zr) structural motif. Synthesis of L(Me)Al(mu-O)M(NMe2)2(mu-O)Al(Me)L [L=CH{N(Ar)(CMe)}2, Ar=2,6-iPr2C6H3; M=Ti (7), Zr (8)] was accomplished by reacting the monometallic hydroxide precursor L(Me)Al(OH) (1) with Ti(NMe2)4 or Zr(NMe2)4 under elimination of Me2NH in good yield. The crystal structural data confirm the trimetallic Al-O-M-O-Al core in both 7 and 8. Preliminary investigation on catalytic activity of these complexes reveals low activity of these complexes in ethylene polymerization as compared to the related oxygen-bridged metallocene-based heterobimetallic complexes L(Me)Al(mu-O)M(Me)Cp2 (M=Ti, Zr) which could be attributed to the relatively lower stability of the supposed cationic intermediate as revealed by DFT calculations.     

Effect of Pyridyl Donors in the Chelation of Aluminum(III), Gallium(III), and Indium(III)

A new preparation of N,N'-bis(2-pyridylmethyl)ethylenediamine-N,N'-diacetic acid (H(2)bped) is reported, and its properties of complexation with Al(III), Ga(III), In(III), and Co(III) are investigated. The molecular structure of the cobalt(III) complex [Co(bped)]PF(6).CH(3)CN.H(2)O (C(20)H(25)CoF(6)N(5)O(5)P) has been solved by X-ray methods; the complex crystallizes in the triclinic space group P&onemacr;, with a = 10.611(2) ?, b = 12.720(2) ?, c = 9.868(1) ?, alpha = 102.70(1) degrees, beta =93.60(1) degrees, gamma = 106.96(1) degrees, and Z = 2. The structure was solved by direct methods and was refined by full-matrix least-squares procedures to R = 0.041 (R(w) = 0.038) for 4312 reflections with I > 3sigma(I). The Co(III) ion is coordinated in a distorted octahedral geometry with an N(4)O(2) donor atom set. The carboxylato oxygen atoms are coordinated trans, while the pyridyl nitrogen atoms are coordinated cis. The largest distortion from octahedral geometry is the N(pyridyl)-Co-N(pyridyl) angle of 107 degrees. Complex formation constants have been measured at 25 degrees C (&mgr; = 0.16 M (NaCl)). log K([M(bped)](+)) (log K([M(bped)(OH)])): M = Al, 10.85 (6.37); M = Ga, 19.89 (15.62); M = In, 22.6 (15.44). A protonated complex was also detected, [Ga(Hbped)](2+), log K = 21.79. The order of stability is In(III) > Ga(III) > Al(III) for the binary species, [M(bped)](+). The solution structures of the complexes have been probed in multinuclear NMR ((1)H, (13)C, (27)Al) studies, and these solution structures are compared with the solid state structure of the cobalt(III) complex. The complexes [In(bped)](+) and [In(bped)(OH)] are proposed to contain 7-coordinate In(III) with water and hydroxide completing the respective coordination spheres. The gallium complexes are proposed to be 6-coordinate: the [Ga(Hbped)](2+) complex contains a nondeprotonated carboxylic acid group which is not coordinated, and [Ga(bped)(OH)] contains a coordinated hydroxide which displaces a carboxylato donor. The [Al(bped)(OH)] complex may be 5-coordinate on the basis of its downfield (27)Al NMR chemical shift, 54 ppm.     

(Fluoren-9-ylidene)methanedithiolato complexes of platinum: synthesis, reactivity, and luminescence

Platinum(II) complexes with (fluoren-9-ylidene)methanedithiolato and its 2,7-di-tert-butyl- and 2,7-dimethoxy-substituted analogues were obtained by reacting different chloroplatinum(II) precursors with the piperidinium dithioates (pipH)[(2,7-R2C12H6)CHCS2] [R = H (1a), t-Bu (1b), or OMe (1c)] in the presence of piperidine. The anionic complexes Q2[Pt{S(2)C=C(C12H6R(2)-2,7)}2] [R = H, (Pr(4)N)(2)2a; R = t-Bu, (Pr4N)(2)2b, (Et4N)(2)2b; R = OMe, (Pr4N)(2)2c] were prepared from PtCl(2), piperidine, the corresponding QCl salt, and 1a-c in molar ratio 1:2:2:2. In the absence of QCl, the complexes (pipH)(2)2b and [Pt(pip)(4)]2b were isolated depending on the PtCl(2):pip molar ratio. The neutral complexes [Pt{S2C=C(C12H6R(2)-2,7)L(2)] [L = PPh(3), R = H (3a), t-Bu (3b), OMe (3c); L = PEt(3), R = H (4a), t-Bu (4b), OMe (4c); L(2) = dbbpy, R = H (5a), t-Bu (5b), OMe (5c) (dbbpy = 4,4'-di-tert-butyl-2,2'-bipyridyl)] were similarly prepared from the corresponding precursors [PtCl2L2] and 1a-c in the presence of piperidine. Oxidation of Q(2)2b with [FeCp2]PF6 afforded the mixed Pt(II)-Pt(IV) complex Q2[Pt2{S2C=C[C12H6(t-Bu)(2)-2,7]}4] (Q(2)6, Q = Et4N+, Pr4N+). The protonation of (Pr4N)(2)2b with 2 equiv of triflic acid gave the neutral dithioato complex [Pt2{S2CCH[C12H6(t-Bu)(2)-2,7]}4] (7). The same reaction in 1:1 molar ratio gave the mixed dithiolato/dithioato complex Pr4N[Pt{S2C=C[C12H6(t-Bu)(2)-2,7]}{S2CCH[C12H6(t-Bu)(2)-2,7]}] (Pr(4)N8) while the corresponding DMANH+ salt was obtained by treating 7 with 2 equiv of 1,8-bis(dimethylamino)naphthalene (DMAN). The crystal structures of 3b and 5c.CH2Cl2 have been solved by X-ray crystallography. All the platinum complexes are photoluminescent at 77 K in CH2Cl2 or KBr matrix, except for Q(2)6. Compounds 5a-c and Q8 show room-temperature luminescence in fluid solution. The electronic absorption and emission spectra of the dithiolato complexes reveal charge-transfer absorption and emission energies which are significantly lower than those of analogous platinum complexes with previously described 1,1-ethylenedithiolato ligands and in most cases compare well to those of 1,2-dithiolene complexes.     

Monomeric Bis(eta(2)-alkyne)copper(I) and -silver(I) Halides, Pseudohalides, and Arenethiolates

The synthesis and characterization of the complexes [(eta(5)-C(5)H(4)SiMe(3))(2)Ti(C&tbd1;CSiMe(3))(2)]MX (M = Cu, X = OTf (2), SC(6)H(5) (4), SC(6)H(4)NMe(2)-2 (5), SC(6)H(4)CH(2)NMe(2)-2 (6), S-1-C(10)H(6)NMe(2)-8 (7), Cl (8), (N&tbd1;CMe)PF(6) (9); M = Ag, X = OTf (3)) are described. These complexes contain monomeric MX entities, which are eta(2)-bonded by both alkyne functionalities of the organometallic bis(alkyne) ligand [(eta(5)-C(5)H(4)SiMe(3))(2)Ti(C&tbd1;CSiMe(3))(2)] (1). The reactions of 2 with the Lewis bases N&tbd1;CPh and N&tbd1;CC(H)=C(H)C&tbd1;N afford the cationic complexes {[(eta(5)-C(5)H(4)SiMe(3))(2)Ti(C&tbd1;CSiMe(3))(2)]Cu(N&tbd1;CPh)}OTf (10) and {[(eta(5)-C(5)H(4)SiMe(3))(2)Ti(C&tbd1;CSiMe(3))(2)]Cu}(2)(N&tbd1;CC(H)=C(H)C&tbd1;N)(OTf)(2) (11), respectively. The X-ray structures of 2, 3, and 6 have been determined. Crystals of 2 are monoclinic, space group P2(1)/c, with a = 12.8547(7) ?, b = 21.340(2) ?, c = 18.279(1) ?, beta = 133.623(5) degrees, V= 3629.7(5) ?(3), Z = 4, and final R = 0.047 for 5531 reflections with I >/= 2.5sigma(I) and 400 variables. The silver triflate complex 3 is isostructural, but not isomorphous, with the corresponding copper complex 2, and crystals of 3 are monoclinic, space group P2(1)/c, with a = 13.384(3) ?, b = 24.55(1) ?, c = 13.506(3) ?, beta = 119.21(2) degrees, V = 3873(2) ?(3), Z = 4, and final R = 0.038 for 3578 reflections with F >/= 4sigma(F) and 403 variables. Crystals of the copper arenethiolate complex 6 are triclinic, space group P&onemacr;, with a = 11.277(3) ?, b = 12.991(6) ?, c = 15.390(6) ?, alpha = 65.17(4) degrees, beta = 78.91(3) degrees, gamma = 84.78(3) degrees, V = 2008(2) ?(3), Z = 2, and final R = 0.079 for 6022 reflections and 388 variables. Complexes 2-11 all contain a monomeric bis(eta(2)-alkyne)M(eta(1)-X) unit (M = Cu, Ag) in which the group 11 metal atom is trigonally coordinated by the chelating bis(eta(2)-alkyne) entity Ti(C&tbd1;CSiMe(3))(2) and an eta(1)-bonded monoanionic ligand X. The copper arenethiolate complexes 4-7 are fluxional in solution.     

Synthesis and structures of selected benzamidinates of Li, Na, Al, Zr and Sn(II) using the C1-symmetric ligands [N(SiMe3)C(C6H4Me-4 or Ph)NPh]-

Several compounds based on the C(1)-symmetric ligands [N(R)C(Ar)NPh]- [abbreviated as B1 (Ar = C(6)H(4)Me-4) or B2 (Ar = Ph), R = SiMe(3)] are reported. They are the crystalline metal benzamidinates [Li(mu:kappa2-B1)(OEt2)](2) (1), [Al(kappa2-B1)2Me] (2), [Al(kappa2-B1)2X] [X = Cl/Me, 1 : 1 (3)], [Sn(kappa2-B1)2] (4), Zr(kappa2-B1)2Cl2 (5), [Zr(kappa2-B1)3Cl] (6), [Na(mu:kappa2-B1)(tmeda)]2 (7), K[B1] (8), Li(B2)(OEt2) (9) and Zr(kappa2-B1)3Cl (10) and the known benzamidine Z-H2NC(C6H4Me-4) = NPh (11). They were prepared by (i) insertion of the nitrile 4-MeC6H4CN (1, 7, 8, 11) or PhCN (9) into the appropriate M-N(R')Ph [R' = R and M = Li (1, 9), Na (7), K (8)] bond and subsequent hydrolysis for 11 [R' = H and M = Li], or (ii) a ligand transfer reaction using the lithium amidinate 1 and Al(Me)2Cl (2, 3), SnCl2 (4) or ZrCl4 (5, 6), or Li(B2) and ZrCl4 (10). The X-ray structures of 1, 2, 3, 4, 6b (i.e..3PhMe) 7, and 11 are presented. Exploratory polymerisation experiments are described, using 2, 5 or 6 as a procatalyst with methylaluminoxane (MAO) (Al : Zr ca. 500 : 1) as promoter. Thus toluene solutions were exposed to C2H4 under ambient conditions; while 2 was unresponsive, 5 and 6 showed modest activity in the formation of polyethylene.     

Hybrid catalysts: the synthesis, structure and ethene polymerisation activity of (salicylaldiminato)(pyrrolylaldiminato) titanium complexes

The mono(salicylaldiminato) complexes Ti{3-tBu-2-(O)C6H3CH=N(R)}Cl3(THF)(where R = C6H5, C6F5) react with the metallated pyrrolylaldiminato ligand, K[2-(C6H5NCH)C4H3N], to afford the first examples of hybrid salicylaldiminato-ligated octahedral titanium complexes; the pre-catalysts give from very high to extremely high ethene polymerisation productivities when activated with MAO.     

Synthesis, structural characterization, reactivity, and thermal stability of [eta(5):sigma-Me2C(C5H4)(C2B10H10)]Ti(R)(NMe2)

Reaction of [eta:(5)sigma-Me2C(C5H4)(C2B10H10)]TiCl(NMe2) (1) with 1 equiv of PhCH2K, MeMgBr, or Me3SiCH2Li gave corresponding organotitanium alkyl complexes [eta:(5)sigma-Me2C(C5H4)(C2B10H10)]Ti(R)(NMe2) (R = CH2Ph (2), CH2SiMe3 (4), or Me (5)) in good yields. Treatment of 1 with 1 equiv of n-BuLi afforded the decomposition product {[eta:(5)sigma-Me2C(C5H4)(C2B10H10)]Ti}2(mu-NMe)(mu:sigma-CH2NMe) (3). Complex 5 slowly decomposed to generate a mixed-valence dinuclear species {[eta:(5)sigma-Me2C(C5H4)(C2B10H10)]Ti}2(mu-NMe2)(mu:sigma-CH2NMe) (6). Complex 1 reacted with 1 equiv of PhNCO or 2,6-Me2C6H3NC to afford the corresponding monoinsertion product [eta:(5)sigma-Me2C(C5H4)(C2B10H10)]Ti(Cl)[eta(2)-OC(NMe2)NPh] (7) or [eta:(5)sigma-Me2C(C5H4)(C2B10H10)]Ti(Cl)[eta(2)-C(NMe2)=N(2,6-Me2C6H3)] (8). Reaction of 4 or 5 with 1 equiv of R'NC gave the titanium eta(2)-iminoacyl complexes [eta:(5)sigma-Me2C(C5H4)(C2B10H10)]Ti(NMe2)[eta(2)-C(R)=N(R')] (R = CH2SiMe3, R' = 2,6-Me2C6H3 (9) or tBu (10); R = Me, R' = 2,6-Me2C6H3 (11) or tBu (12)). The results indicated that the unsaturated molecules inserted into the Ti-N bond only in the absence of the Ti-C(alkyl) bond and that the Ti-C(cage) bond remained intact. All complexes were fully characterized by various spectroscopic techniques and elemental analyses. Molecular structures of 2, 3, 6-8, and 10-12 were further confirmed by single-crystal X-ray analyses.