杂环膦亚胺钛配合物的合成及催化乙烯聚合（英文）

首先合成单取代和双取代杂环膦化合物R-PPh_2[R=2-吡啶基(3a),2-噻吩基(3b),2-呋喃基(3c)]和Ph_2P-R'-PPh_2[R'=2,6-吡啶基(6a),2,5-噻吩基(6b),2,5-呋喃基(6c)].然后与叠氮三甲基硅烷发生Staudinger反应生成相应的杂环膦亚胺配体R-PPh_2(NSiMe_3)和(Me_3SiN)Ph_2P-R'-PPh2(NSiMe_3).最后与环戊二烯三氯化钛反应脱去三甲基氯硅烷后得到具有烯烃聚合催化活性的杂环膦亚胺钛配合物.所有配合物结构都经过核磁的确认,为了进一步确定配合物分子结构,利用单晶X射线衍射解析了所有钛配合物的晶体结构.在助催化剂甲基铝氧烷(MAO)活化作用下,双钛中心配合物6a~6c比单钛中心类似配合物3a~3c表现出更高的催化乙烯聚合活性,所得聚合物具有较宽分子量分布呈双峰分布,6b在较低聚合温度下就可以制备超高分子量聚乙烯.     

三叔丁基膦亚胺苯氧钛配合物及其乙烯聚合性能

四种不同基团取代的苯酚锂盐分别与三叔丁基膦亚胺三氯化钛进行反应,制得相应三叔丁基膦亚胺苯氧钛配合物(t-Bu_3)PNTi(OAr)Cl_2[OAr=O-C_6H_5(4a),O-2,6-Me_2C_6H_3(4b),O-2,6-i-Pr_2C_6H_3(4c)和O-2,6-t-Bu_2C_6H_3(4d)],产物均借助~1H NMR,~(13)C NMR,~(31)P NMR及元素分析进行了结构表征,并利用X射线单晶衍射确定了配合物三叔丁基膦亚胺三氯化钛(3),4b和4d的分子结构.在助催化剂甲基铝氧烷(MAO)作用下,4a~4d对乙烯聚合均表现出高催化活性,并随配合物空间位阻增加而升高.4c热稳定性好,通过控制聚合反应条件,由此可以得到不同分子量及分子量分布的聚乙烯产物.     

含溴α-二亚胺镍(Ⅱ)配合物的合成、表征及催化乙烯聚合反应

合成了一种新型含溴α-二亚胺及其镍配合物,采用<'1>H NMR、<'13>C NMR、FTIR、元素分析和XPS等方法进行表征.用配合物作为催化剂,以甲基铝氧烷(MAO)为助催化剂催化乙烯聚合得到高支化度的聚乙烯,并研究了聚合条件(如AL/Ni摩尔比、聚合温度以及配体结构)对催化活性的影响,结果表明,在反应温度为25...     

水杨醛亚胺镍配合物催化乙烯与甲基丙烯酸甲酯的共聚反应

以4种基于水杨醛亚胺配体的镍配合物bis[N-(2,6-diisopropylphenyl)salicylaldiminate]-nickel(Ⅱ)(C1), bis[N-(2,6-diisopropylphenyl)-3-methylsalicylaldiminate]-nickel(Ⅱ)(C2), bis[N-(2,6-diisopropylphenyl)-3-isopropylsalicylaldiminate]-nickel(Ⅱ)(C3)和[N-(2,6-diisopropylphenyl)-3-isopropylsalicylaldiminate]-nickel(Ph)(PPh₃)(C4)为催化剂, 在甲基铝氧烷(MAO)作用下, 对乙烯与甲基丙烯酸甲酯(MMA)进行催化共聚. 以C3为模型催化剂, 研究了Al/Ni摩尔比、 聚合温度、 聚合时间等对共聚反应的影响. 在最佳的聚合条件下, 探索了不同的催化剂结构对共聚反应的影响. 结果表明, 对于双(水杨醛亚胺)镍配合物, C2的活性高于C1和C3, 为13.1 kg/(mol Ni·h), 而C3的插入率最低, 为14.1%. 对于具有相同配体不同结构的配合物C3和C4, 含双水杨醛亚胺配体的C3的催化活性高于含单水杨醛亚胺配体的C4, 而两者在共聚单体MMA的插入率方面差别不大. 对所得共聚物微观结构和热性能进行了表征.     

氧桥联双核钛、镍配合物的合成及催化制备双峰聚乙烯

从2种氧原子桥联双膦化合物双(2-二苯基膦苯基)醚(1a)和4,5-双(二苯基膦)-9,9-二甲基氧杂蒽(1b)出发,合成氧原子桥联双膦亚胺钛、镍配合物.在甲苯中回流条件下首先将化合物1a和1b与叠氮三甲基硅烷发生Staudinger反应,分别生成单和双膦亚胺前驱体2a和2b.然后再与环戊二烯基三氯化钛反应,脱去三甲基氯硅烷后得到相应膦亚胺过渡金属钛配合物3a和3b.单钛中心配合物3b进一步与乙二醇二甲醚溴化镍反应生成钛-镍异核双中心配合物4b.通过1H NMR,13C NMR,31P NMR,FTIR及元素分析对产物进行了表征,并利用X射线单晶衍射分析确定了配合物3a和3b的分子结构.在助催化剂甲基铝氧烷(MAO)作用下,配合物3a和4b对乙烯聚合均表现出较高的催化活性,其中双钛中心配合物3a催化得到较宽分子量的聚乙烯产物,而异核双中心配合物4b催化得到呈双峰分布的聚乙烯产物.     

超支化分子桥联水杨醛亚胺镍配合物的合成及对乙烯齐聚反应的催化性能

合成了一种具有超支化结构的新型水杨醛亚胺配体及其Ni(Ⅱ)配合物, 利用元素分析、 电喷雾电离质谱(ESI-MS)、 傅里叶变换红外光谱(FTIR)、 紫外-可见光谱(UV-Vis)、 氢核磁共振谱(¹H NMR)和碳核磁共振谱(¹³C NMR)对其结构进行了表征. 以甲基铝氧烷(MAO)为助催化剂, 考察了超支化水杨醛亚胺镍配合物对乙烯齐聚反应的催化活性及聚合条件(Al/Ni摩尔比、 聚合温度)对催化剂活性及聚合产物分布的影响. 结果表明, 在反应温度为25 ℃、 Al/Ni摩尔比为500时, 该催化剂的活性最高达到5.59×10⁵ g/(mol Ni·h), 得到的聚合产物为全馏分烯烃, 其中高碳烯烃C₁₀~C₁₈的含量最高达91%.     

α-萘基丁二亚胺氯化镍/MAO制备双(宽)峰聚乙烯

合成了一种新型α 二亚胺镍配合物———α 萘基丁二亚胺氯化镍 ,此配合物作为催化剂在MAO的活化下催化乙烯聚合得到支化聚乙烯 ,聚合活性高达 7 18× 10 5gPE molNi·h ,1 3C NMR、FTIR测试结果表明制备的聚乙烯含有末端双键 ;GPC结果表明所制备的聚乙烯分子量呈双 (宽 )峰分布 ,其原因有两个 ,一是此催化剂能产生分子量较低的α 烯烃 ,在聚合过程中一部分α 烯烃会“就地”与乙烯原位共聚形成分子量较高的聚合物 ,二是此催化剂存在立体异构体 ,而不同异构体在MAO活化下形成的活性中心的配位环境不同 ,因而得到的聚乙烯的分子量也不同 .研究了聚合温度、聚合压力、铝镍摩尔比 (nAl nNi)对催化活性、聚乙烯分子量、支化度的影响 .聚乙烯的分子量随聚合温度的升高而下降 ,支化度增大 ,熔点则降低 .     

[N^N^O]钴配合物催化丁二烯立体选择性聚合的研究

合成并表征了一系列带有[2-(4,5-二苯基-2-咪唑基)-1-苯亚胺基]苯酚配体([N^N^O]三齿配体)的二氯化钴配合物(1~4),并研究了这些配合物对丁二烯溶液聚合的催化性能.研究结果表明,助催化剂的种类对丁二烯聚合的催化活性和产物性能有显著的影响,倍半乙基氯化铝(EASC)为最佳的助催化剂.在EASC的活化作用下,该催化体系引发丁二烯单体聚合,15 min内丁二烯单体的转化率可达92.7%,产物聚丁二烯中顺式1,4-结构的含量高达97.4%.并详细研究了助催化剂的用量、聚合的温度、配体上不同取代基等对丁二烯聚合行为的影响,包括丁二烯单体的转化率、产物聚丁二烯的分子量与分子量分布及微观结构.通过凝胶渗透色谱法(GPC)对聚合产物的分子量及分子量分布进行了表征,核磁共振氢谱(1H-NMR)和碳谱(13CNMR)分析结果表明所得聚合物具有高的顺式1,4-结构含量(97%左右).     

"一锅法"N-(2-苯甲酰胺苯基)-水杨醛亚胺/TiCl4·2THF催化乙烯聚合

报道了4个含苯甲酰胺取代的水杨醛亚胺配体: N-(2-苯甲酰胺苯基)-水杨醛亚胺(L1)、 N-(2-苯甲酰胺苯基)-3-甲基水杨醛亚胺(L2)、 N-(2-苯甲酰胺苯基)-3-叔丁基水杨醛亚胺(L3)和N-(2-苯甲酰胺苯基)-3,5-二溴水杨醛亚胺(L4)的合成, 采用 ¹H NMR和HRMS对其结构进行了表征. 在助催化剂甲基铝氧烷(MAO)作用下, 以L3与TiCl₄·2THF为模型催化体系, 在最佳陈化条件(陈化温度为25 ℃, 陈化时间为30 min, 配体与TiCl₄·2THF的摩尔比3∶1)下, 考察了L1~L4/TiCl₄·2THF催化体系Al/Ti摩尔比、 反应时间、 反应温度和聚合压力, 以及配体结构等对乙烯聚合的影响. 结果表明, 随着在水杨醛骨架上氧原子邻位取代基位阻的增大, 催化体系的活性及所得聚乙烯的分子量均有增加, 其中以L3的催化活性最高, 达到224 kg PE/(mol Ti?h). 采用高温 ¹H NMR, ¹³C NMR, GPC-IR和DSC等对由不同配体L1~L4/TiCl₄·2THF得到的聚乙烯样品的微观结构与热性能进行了分析与表征, 结果显示样品为线性高密度聚乙烯, M_n=5.9×10 ⁴~11.9×10 ⁴, 分子量分布(PDI)为21.9~72.1.     

吡啶/吡咯亚胺型钴、镍配合物合成及其催化甲基丙烯酸甲酯聚合研究

以冰醋酸/微波辐射催化2-乙酰基吡啶/吡咯与对苯二胺、卡巴肼发生Schiff碱缩合反应得到系列配体L1～L4,在甲醇/四氢呋喃中进一步与钴/镍氯化物反应获得配合物1～8。用元素分析、核磁氢谱、红外、紫外光谱和X-射线单晶衍射等手段对产物进行全面结构表征发现,配体L1～L3为二胺桥连的双亚胺吡啶/吡咯结构,L4为单亚胺吡咯结构,配合物1～6均为双核配合物,而7、8为单核配合物。配体合成实验中发现L1的产率最高,达到89.8%,说明苯胺与直链胺相比亲核性更强,更有利于产物的生成。通过系统研究配合物1～8对甲基丙烯酸甲酯(MMA)聚合催化行为与催化剂结构、聚合反应条件的关系发现,当聚合时间为6 h,温度为90℃,单体与催化剂比例n(M)/n(Ni)为3000:1,主催剂和引发剂比例n(Ni)/n(AIBN)为2:1时,由2-乙酰基吡啶与对苯二胺缩合形成的双亚胺配体Ni(Ⅱ)配合物的催化活性最高,可达到4.3281×10⁴ g·mol^-1·h^-1。     

Cationic rare-earth metal trimethylsilylmethyl complexes supported by THF and 12-crown-4 ligands: synthesis and structural characterization

To expand the limited range of rare-earth metal cationic alkyl complexes known, a series of mono- and dicationic trimethylsilylmethyl complexes supported by THF and 12-crown-4 ligands with [BPh4]-, [BPh3(CH2SiMe3)]-, [B(C6F5)4]-, [B(C6F5)3(CH2SiMe3)]-, and [Al(CH2SiMe3)4]- anions were prepared from corresponding neutral precursors [Ln(CH2SiMe3)3Ln] (Ln = Sc, Y, Lu; L = THF, n = 2 or 3; L = 12-crown-4, n = 1) as solvent-separated ion pairs. The syntheses of the monocationic derivatives [Ln(CH2SiMe3)2(12-crown-4)n(THF)m]+[A]- are all high yielding and proceed rapidly in THF solution at room temperature. A "one pot" procedure using the neutral species directly for the syntheses of a number of lutetium and yttrium dicationic derivatives [Ln(CH2SiMe3)(12-crown-4)n(THF)m]2+[A]-2 with a variety of different anions, a class of compounds previously limited to just a few examples, is presented. When BPh3 is used to generate the ion triple, the presence of 12-crown-4 is required for complete conversion. Addition of a second equiv of 12-crown-4 and a third equiv of [NMe2PhH]+[B(C6F5)4]- abstracts a third alkyl group from [Ln(CH2SiMe3)(12-crown-4)2(THF)x]2+[B(C6F5)4]-2 (Ln = Y, Lu). X-ray crystallography and variable-temperature (VT) NMR spectroscopy reveal a structural diversity within the known series of neutral 12-crown-4 supported tris(trimethylsilylmethyl) complexes [Ln(CH2SiMe3)3(12-crown-4)] (Ln = Sc, Y, Sm, Gd-Lu) in the solid and solution states. The X-ray structure of [Sc(CH2SiMe3)3(12-crown-4)] exhibits incomplete 12-crown-4 coordination. VT NMR spectroscopy indicates fluxional 12-crown-4 coordination on the NMR time scale. X-ray crystallography of only the second structurally characterized dicationic rare-earth metal alkyl complex [Y(CH2SiMe3)(12-crown-4)(THF)3]2+[BPh4]-2 shows exocyclic 12-crown-4 coordination at the 8-coordinate metal center with well separated counteranions. 11B and 19F NMR spectroscopy of all mono- and dicationic rare-earth metal complexes reported demonstrate that the anions are symmetrical and noncoordinating on the NMR time scale. A series of trends within the 1H and 13C{1H} NMR resonances arising from the Ln-CH2 groups and, in the case of yttrium, the 1JYC coupling constants at the Y-CH2 group and the 89Y chemical shift values are discussed.     

Rare earth metal complexes bearing thiophene-amido ligand: synthesis and structural characterization

2,6-diisopropyl-N-(2-thienylmethyl)aniline (H2L) has been prepared, which reacted with equimolar rare earth metal tris(alkyl)s, Ln(CH2SiMe3)3(THF)2, afforded rare earth metal mono(alkyl) complexes, LLn(CH2SiMe3)(THF)3 (:Ln=Lu; :Ln=Y). In this process, H2L was deprotonated by one metal alkyl species followed by intramolecular C-H activation of the thiophene ring to generate dianionic species L2- with the release of two tetramethylsilane. The resulting L2- combined with three THF molecules and an alkyl unit coordinates to Y3+ and Lu3+ ions, respectively, in a rare N,C-bidentate mode, to generate distorted octahedron geometry ligand core. Whereas, with treatment of H2L with equimolar Sc(CH2SiMe3)3(THF)2, a heteroleptic complex (HL)(L)Sc(THF) () was isolated as the main product, where the dianionic L2- species bonds to Sc3+ via chelating N,C atoms whilst the monoanionic HL connects to Sc3+ in an S,N-bidentate mode. All complexes have been characterized by NMR spectroscopy and X-ray diffraction analysis.     

Synthesis and characterization of heterobimetallic oxo-bridged aluminum-rare earth metal complexes

Reaction of the aluminum hydroxide LAl(OH)[C(Ph)CH(Ph)] (1, L = HC[(CMe)(NAr)](2), Ar = 2,6-iPr(2)C(6)H(3)) with Y(CH(2)SiMe(3))(3)(THF)(2) yielded the oxo-bridged heterobimetallic yttrium dialkyl complex LAl[C(Ph)CH(Ph)](μ-O)Y(CH(2)SiMe(3))(2)(THF)(2) (2). Alkane elimination reaction of 2 with 2-(imino)pyrrole [NN]H ([NN]H = 2-(ArN═CH)-5-tBuC(4)H(2)NH) afforded the yttrium monoalkyl complex LAl[C(Ph)CH(Ph)] (μ-O)Y(CH(2)SiMe(3))[NN](THF)(2) (5). Alternatively, 5 can be prepared in high yield by reaction of 1 with [NN]Y(CH(2)SiMe(3))(2)(THF)(2) (3). The analogous samarium alkyl complex LAl[C(Ph)CH(Ph)](μ-O)Sm(CH(2)SiMe(3))[NN](THF)(2) (6) was prepared similarly. Reactions of 5 and 6 with 1 equiv of iPrOH yielded the corresponding alkoxyl complexes 7 and 8, respectively. The molecular structures of 3, 6, and 8 have been determined by X-ray single-crystal analysis. Complexes 2, 3, 5, 7, and 8 have been investigated as lactide polymerization initiators. The heterobimetallic alkoxyl 8 is highly active to yield high molecular weight (M(n) = 6.91 × 10(4)) polylactides with over 91% conversion at the lactide-to-initiator molar ratio of 2000.     

Protonation of a lanthanum phosphide-alkyl occurs at the P-La not the C-La bond: isolation of a cationic lanthanum alkyl complex

Protonation of the heteroleptic, cyclometalated lanthanum phosphide complex [((Me3Si)2CH)(C6H4-2-CH2NMe2)P]La(THF)[P(C6H4-2-CH2NMe2)(CH(SiMe3)(SiMe2CH2))] with [Et3NH][BPh4] yields the cationic alkyllanthanum complex [(THF)4La[P(C6H4-2-CH2NMe2)(CH(SiMe3)(SiMe2CH2))]][BPh4].     

Synthetic and structural experiments on yttrium, cerium and magnesium trimethylsilylmethyls and their reaction products with nitriles; with a note on two cerium beta-diketiminates

The yttrium, cerium and magnesium bis(trimethylsilyl)methyls [Ln[CH(SiMe3)2]3][Ln = Y (1), Ce (2)], and the known compound Mg[[CH(SiMe3)2]2 (C) and [Mg(mu-Br)[CH(SiMe3)2](OEt2)]2 (D) formed the crystalline nitrile adducts [1(NCBut)2] (5), [2(NCPh)] (6), [C(NCR)2][R = But (8), Ph (9), C6H3Me2-2,6 (10)] and [Mg(mu-Br)[CH(SiMe3)2](NCR)]2 [R = But (11), Ph (12), C6H3Me2-2,6 (13)], rather than beta-diketiminato-metal insertion products. The beta-diketiminato-cerium complex [Ce[(N(SiMe3)C(C6H4But-4))2CH][N(SiMe3)2]2] (16) was obtained from [Ce[N(SiMe3)2]3] and the beta-diketimine H[[N(SiMe3)C(C6H4But-4)]2CH]]. The cerium alkyl 2 and [Ln[CH(SiMe3)(SiMe2OMe)]3][Ln = Y (3), Ce (4)] were obtained from the appropriate lithium alkyl precursor and [Ce(OC6H2But2-2,6-Me-4)3] or LnCl3, respectively. Heating complex 3 with benzonitrile in toluene afforded 2,2-dimethyl-4,6-diphenyl-5-trimethylsilyl-1,3-diaza-2-silahexa-1,3-diene (7), a member of a new class of heterocycles. The X-ray structures of the crystalline compounds, D, [Mg[CH(SiMe3)2]2(OEt2)2], the known [Ce(Cl)[(N(SiMe3)C(Ph))2CH]2] (E) and 16 are reported. The cerium alkyl (like 1) has one close Ce...C contact for each ligand, attributed to a gamma-C-Ce agostic interaction. The Ln alkyls and have a trigonal prismatic arrangement of the chelating ligands (each of the same chirality at Calpha) around the metal. In an arene solution at 313 K exists as two isomers, as evident from detailed NMR spectroscopic experiments.     

Synthesis and characterization of organo-scandium and yttrium complexes stabilized by phosphinoamide ligands

Addition of three equivalents of phosphinoamine, (ArNHP(i)Pr(2)) [Ar = 3,5-dimethylphenyl] to M(CH(2)SiMe(3))(3)(THF)(2) [M = Sc, Y] precursors gives complexes of the form (ArNP(i)Pr(2))(3)M(THF) [M = Sc, Y]. In the case of scandium, addition of Sc(CH(2)SiMe(3))(3)(THF)(2) to (ArNP(i)Pr(2))(3)Sc(THF) affords (ArNP(i)Pr(2))(2)Sc(CH(2)SiMe(3))(THF), which has been isolated and structurally characterized. In contrast, addition of Y(CH(2)SiMe(3))(3)(THF)(2) to (ArNP(i)Pr(2))(3)Y(THF) generates a distribution of phosphinoamide-containing products consistent with the formulations (ArNP(i)Pr(2))(2)Y(CH(2)SiMe(3))(THF) and (ArNP(i)Pr(2))Y(CH(2)SiMe(3))(2)(THF), as ascertained using NMR spectroscopy. Attempts to react the alkyl-containing phosphinoamide complexes with small molecules such as H(2) led to disproportionation type processes.     

The first structurally characterized cationic lanthanide-alkyl complexes

Reaction of rare earth metal-alkyl complexes [Ln(CH2SiMe3)3(THF)2](Ln = Y, Lu) with B(C6X5)3(X = H, F) in the presence of crown ethers gives crystallographically characterized ion pairs [Ln(CH2SiMe3)2(CE)(THF)n]+[B(CH2SiMe3)(C6X5)3]-(CE = [12]-crown-4, n = 1; CE = [15]-crown-5 and [18]-crown-6, n = 0).     

Hydrogenation of C=C and C=N Bonds of the Amide-Imine Ligand in the Metal Coordination Sphere in the Reaction of Yttrium Bis(alkyl) Complex [2,6-iso-Pr2C6H3NC(=CH2)C(Me)=NC6H3-iso-Pr2-2,6]Y(CH2SiMe3)2(THF) with Molecular Hydrogen

Russian Journal of Coordination Chemistry - On treatment of the yttrium bis(alkyl) complex [ArNC(=CH2)C(Me)=NAr]Y(CH2SiMe3)2(THF) (I, Ar = C6H3-iso-Pr2-2.6) containing an amide-imine ligand, with...     

Metal versus ligand alkylation in the reactivity of the (bis-iminopyridinato)Fe catalyst

The alkylation of the Brookhart-Gibson {2,6-[2,6-(i-Pr)2PhN=C(CH3)]2(C5H3N)} FeCl2 precatalyst with 2 equiv of LiCH2Si(CH3)3 led to the isolation of several catalytically very active products depending on the reaction conditions. The expected dialkylated species {2,6-[2,6-(i-Pr)2PhN=C(CH3)]2}(C5H3N)Fe(CH2SiMe3)2 (2) was indeed the major component of the reaction mixture. However, other species in which alkylation occurred at the pyridine ring ortho position, {2,6-[2,6-(i-Pr)2PhN=C(CH3)]2-2-CH2SiMe3}(C5H3N)Fe(CH2SiMe3) (1), and at the imine C atom, {2-[2,6-(i-Pr)2PhN=C(CH3)]-6-[2,6-(i-Pr)2PhNC(CH3)(CH2 SiMe3)](C5H3N)}Fe(CH2SiMe3) (3), have also been isolated and fully characterized. In addition, deprotonation of the methyl-imino functions and formation of a new divalent Fe catalyst {[2,6-[2,6-(i-Pr)2PhN-C=(CH2)]2(C5H3N)}Fe(mu-Cl)Li(THF)3 (4) also occurred depending on the reaction conditions. In turn, the formation of 4 might trigger the reductive coupling of two units through the methyl-carbon wings. This process resulted in the one-electron reduction of the metal center, affording a dinuclear Fe(I) alkyl catalyst {[{[2,6-(i-Pr)2C6H5]N=C(CH3)}(C5H3N){[2,6-(i-Pr)26H5]N=CCH2}Fe(CH2SiMe3)]}2 (5). Different from other metal derivatives, complex 5 could not be prepared from the monodeprotonated version of the ligand. Its reaction with a mixture of FeCl2 and RLi afforded instead [{2,6-[2,6-(i-Pr)2PhN-C=(CH2)]2(C5H3N)}FeCH2Si(CH3)3][Li(THF)4] (6) which is also catalytically active. All of these high-spin species have been shown to have high catalytic activity for olefin polymerization, producing polymers of two distinct natures, depending on the formal oxidation state of the metal center.     

Reduction of carbodiimides by samarium(II) bis(trimethylsilyl)amides-formation of oxalamidinates and amidinates through C-C coupling or C-H activation

The reaction of [Sm{N(SiMe3)2}2(THF)2] (THF=tetrahydrofuran) with carbodiimides RN=C=NR (R=Cy, C6H3-2,6-iPr2) led to the formation of dinuclear SmIII complexes via differing C-C coupling processes. For R=Cy, the product [{(Me3Si)2N}2Sm(micro-C2N4Cy4)Sm{N(SiMe3)2}2] (1) has an oxalamidinate [C2N4Cy4]2- ligand resulting from coupling at the central C atoms of two CyNCNCy moieties. In contrast, for R=C6H3-2,6-iPr2, H transfer and an unusual coupling of two iPr methine C atoms resulted in a linked formamidinate complex, [{(Me3Si)2N}2Sm{micro-(RNC(H)N(Ar-Ar)NC(H)NR)}Sm{N(SiMe3)2}2] (2) (Ar-Ar=C6H3-2-iPr-6-C(CH3)2C(CH3)2-6'-C6H3-2'-iPr). Analogous reactions of RN=C=NR (R=Cy, C6H3-2,6-iPr2) with the SmII "ate" complex [Sm{N(SiMe2)3Na] gave 1 for R=Cy, but a novel C-substituted amidinate complex, [(THF)Na{N(R)C(NR)CH2Si(Me2)N(SiMe3)}Sm{N(SiMe3)2}2] (3), for R=C6H3-2,6-iPr2, via gamma C-H activation of a N(SiMe3)2 ligand.