Synthesis and Characterization of New Macrocyclic Cu（Ⅱ） Complexes from Various Diamines, Copper（Ⅱ） Nitrate and 1,4-Bis（2-formylphenoxy）butane

Six new macrocyclic complexes were synthesized by a template reaction of 1,4-bis（2-formylphenoxy）butane with diamines and Cu（NO3）2·3H2O and their structures were proposed on the basis of elemental analysis, FT-IR, UV-Vis, magnetic susceptibility measurements, molar conductivity measurements and mass spectra. The metal to ligand molar ratios of the Cu（Ⅱ） complexes were found to be 1 ： 1. The Cu（Ⅱ） complexes are 1 ： 2 electrolytes as shown by their molar conductivities （∧m） in DMF at 10^-3 mol·L^-1. Due to the existence of free ions the Cu（Ⅱ） complexes are electrically conductive. Their configurations were proposed to be probably distorted octahedral.     

Syntheses of Some New Group 4 non-Cp Complexes Bearing Schiff-base, Thiophene Diamide Ligands Respectively and Their Catalytic Activities for a-Olefin Polymerization

Totally sixteen new titanium and zirconium non-Cp complexes supported by Schiff-base, or thiophene diamide ligands have been synthesized. The complexes are obtained by the reaction of M(OPr-i)4(M=Ti,Zr) with the corresponding Schiff-base ligand in 1:1 molar ratio in good yield. The thiophene diamide titanium complex has been prepared from trimethylsilyl amine [N,S,N] ligand and TiCl4 in toluene at 120℃. All complexes are well charac-terized by ^1H NMR, IR, MS and elemental analysis. When activated by excess methylaluminoxane (MAO), complexes show moderate catalytic activity for ethylene polymerization, and complex If (R^1=CH3,R^2=Br) exhibits the highest activity for ethylene and styrene polymerization. When the complexes were preactivated by triethylaluminum (TEA), both polymerization activities and syndiotacticity of the polymers were greatly improved.     

A Novel Divalent Ytterbium Complex Supported by a Bridged Diamide Ligand： Synthesis and Structure of [{Me2Si（NPh ）2Yb（THF）2}（μ3-CI）（μ4-CI）{Li（TH F） }2]2·2THF

The reaction of anhydrous YbCl3 with 1 equiv, of Li2Me2Si（NPh）2 in THF, after workup, yielded a ytterbium（Ⅲ） chloride [{Me2Si（NPh）2Yb}（μ2-CI）（TMEDA）]2·3PhMe （1） （TMEDA=tetramethylethanediamine）. The same reaction followed by treatment with Na-K alloy afforded a new ytterbium（H） complex supported by a bridged diamide with four coordinated LiC1 molecules, [{Me2Si（NPh）2Yb（THF）2}（μ3-CI）（μ4-CI）{Li（THF）}2]2·2THF （2） in high yield. Both complexes were structurally characterized by X-ray analysis to be dimers. Complex 1 was a chlorine-bridged dimer with ytterbium in a distorted octahedral geometry. In complex 2 two [Me2Si（NPh）2Yb（THF）2]- （μ3-CI）[Li（THF）]2 moieties were connected with each other by two μ4-CI bridges to form a ＂chair-form＂ framework.     

Selective 3,4-Polymerization Mechanism of Isoprene Catalyzed by Rare Earth Alkyl Complexes

The mechanism of selective 3,4-polymerization reaction of isoprene catalyzed by the rare earth lutecium（Ⅲ） alkyl complexes [2,6-Me2Ph-N-CH2-C（CH2SiMe3）=N-PhMe2-2,6]Lu（CH2SiMe3）2（THF）was investigated by means of the M06/sdd method with solvation effects taken into account.The results show that the structure of the catalyst core remained almost unchanged as the isoprene molecules were alternatively inserted into the complex at two opposite sides.The Gibbs free energies of the coordination complexes,transition state and intermediates indicate that all the isoprene molecules prefer to insert into the complex with the 3,4-polymerization selectivity as catalyzed by the catalyst,which is consistent with the experimental observations.It is found that the insertion reaction of each isoprene is exothermic,which comes mainly from the coordination of the isoprene molecule to the lutecium（Ⅲ） atom.The solvation effects were confirmed important in predicting the Gibbs free energies of the present reaction system.     

Metallotricycle of Lanthanide Supported by a Bridging Diamide: Syntheses and Molecular Structures of {Li(THF)3[LnCl(μ2-trans-1,2-(NSiMe3)2C6H10)(μ2-Cl)]}2•2THF (Ln＝Yb, Nd)

The reactions of dilithium salt of trans-1,2-bis（trimethylsilylamino）cyclohexane with anhydrous lanthanide trichlorides LnCl3 （Ln = Yb, Nd） in THF afforded the dianionic binuclear tricycles of lanthanide chlorides {Li（THF）3[LnCl（μ2-trans-1,2-（NSiMe3）2C6H10）（μ2-Cl）]}2·2THF （Ln=Yb 1, Nd 2） in moderate yields. Both of the bridged complexes were characterized by elemental analysis, IR spectroscopy and single-crystal X-ray diffraction. Crystal structural analysis shows that the two complexes are the analogues which have a tricyclic framework built by two bridged lanthanide metals, four nitrogens and four carbons from two diamide ligands. Each lanthanide metal coordinates to three nitrogen atoms and two chlorines to form a distorted trigonal bipyramid and connects with a lithium by a bridging chlorine.     

Characterization, Crystal Structure and Initial DNA Binding Interaction of Two Cu（Ⅱ） Complexes with 4,5-Diazafluoren-9-one

Two new complexes [Cu（dafo）2（en）]（ClO4）2·2H2O （en=NH2CH2CH2NH2） 1 and [Cu（dafo）2（dap）]（ClO4）2·2H2O [dap=NH2CH2CH（CH3）NH2] 2 （dafo=4,5-diazafluoren-9-one） have been synthesized and characterized by elemental analysis, IR and UV spectra. Meanwhile, the complex 1 has been characterized by single crystal X-ray diffraction analysis. The initial DNA binding interactions of the complexes 1 and 2 have been investigated by UV spectra, emission spectra and cyclic voltammogram. Concluding the results of three methods used to measure the interaction of complexes 1 and 2 with DNA, the action mode of the two complexes with DNA is intercalation, and character of ligands and steric effect may affect the interaction of the complexes with DNA.     

Copolymerization of Ethylene with lO-Undecen-l-ol Using Highly Active Vanadium（III） Precatalysts Bearing Bis（imino）pyrrolyl Ligands

The copolymerizations of ethylene with 10-undecen-1-ol have been investigated using vanadium precatalysts, bis（imino）pyrrolyl vanadium（Ⅲ） complexes 1-3, 2,5-C4H2N（CH=NR）2VCl2（THF）2 [R = C6H5 （1）, 2,6-iPr2C6H3 （2）, C6F5 （3）], and the iminopyrrolyl and b-diketiminate ones for comparison. The polar monomer was pretreated by diethylaluminium chloride （present also as the cocatalyst） before the copolymerization. The monomer reactivity ratios were evaluated using the Fineman-Ross method. The ligand structure considerably influenced the catalytic activity and tolerance towards the polar monomer, the polar monomer incorporation and the molecular weights of the resultant copolymers. The bis（imino）pyrrolyl vanadium complexes exhibited promising catalytic performance for the copolymerization, and a high catalytic activity up to 3.84 kg/mmolv·h with a high comonomer incorporation of 14.0 mol% was achieved by complex 3 under mild conditions.     

Synthesis and Structural Characterization of Alkali Metal Guanidinates

Reactions of 1,3-diisopropylcarbodiimide with alkali metal amides, MN（SiMe3）2 （M=Li or Na） in hexane or THF produced the alkali metal guanidinates { （i-PrN）2C [N（SiMe3）2]Li }2 （1） and { （i-PrN）2C[N（SiMe3）2]Na（THF） } 2 （2） in nearly quantitative yields. Both complexes 1 and 2 were well characterized by elemental analysis, IR spectra, ^1H and ^13C NMR spectra, and X-ray diffraction. It was found that the guanidinates adopt different coordination modes in these complexes.     

Zinc Complexes Supported by N,N-Dimethylaniline-arylamido Ligands： Synthesis,Characterization and Catalytic Properties for Ring-opening Polymerization of L-Lactide

The reaction of bidentate N,N-dimethylaniline-arylamido ligands,o-C6H4NMe2（CH2NHAr）（Ar =Ph,1a;2,6-Me2C6H3,1b; 2,6-Et2C6H3,1c; 2,6-ipr2C6H3,1d） with ZnEt2 yields the complexes o-C6H4（NMe2）（CH2NAr）ZnEt （2a-2d）,respectively.All the complexes were characterized by 1H and 13C NMR spectroscopy and elemental analyses.It was found that all the zinc complexes were efficient catalysts for the ring-opening polymerization of L-lactide in the presence of benzyl alcohol with good molecular weight control and narrow polydispersity.     

Syntheses of(C_8H_8)Ln(C_9H_7)·(THF)_2(Ln=Pr,Nd)and crystal structure of(C_8H_8)Pr(C_9H_7)·(THF)_2

This paper reports two lanthanide complexes of formula (C_9H_7)Ln(C_8H_8)·(THF)_2 whereLn is Pr or Nd,C_9H_7 is indenyl,and C_8H_8 is cyclooctatetraene (COT).The complexes were preparedby the reaction of LnCl_3 with K(C_9H_7) and K_2(C_8H_8) in THF.(C_9H_7)Pr(C_8H_8)·(THF)_2 crystallizes inTHF at - 15℃ in the monoclinic space group P2_1:with unit cell dimensions a=8.446(0),b=10.083(2),c=13.407(3),β=105.48(1)°,V=1100.43(35)~3,Dc=1.52g/cm~3 and Z=2.The final R valueis 0.033,R_w value is 0.030,respectively.In (C_9H_7)Pr(C_8H_8)·(THF)_2 a five-membered ring centroid ofC_9H_7,the C_8H_8 ring centroid and the two oxygen atoms from the two THF molecules form a distortedtetrahedral geometry around the metal.     

Synthesis,Structures and DFT Studies of Imido‐bridged and (Bis)ligand‐coordinated Titanium Complexes

Syntheses and structures of five imido‐bridged dinuclear titanium complexes and two (bis)ligand‐coordinated mononuclear titanium complexes are reported. Addition of 1 or 2 equiv. of Schiff base ligand (((1H‐pyrrol‐2‐yl)methylene)amino)‐2,3‐dihydro‐1H‐inden‐2‐ol (H₂L) to Ti(NMe₂)₄ resulted in transamination with 4 equiv. of dimethylamides generating a (bis)ligand‐coordinated complex Ti(L)₂ ( 1 ). Treatment of Ti(NMe₂)₄ with 1 equiv. of ^tBuNH₂ followed by addition of 1 equiv. of H₂L afforded an imido‐bridged complex [Ti(L)(N^tBu)]₂ ( 2 ). 1:1:1:1 reaction of Ti(NMe₂)₄/RNH₂/H₂L/py(or phen) produced imido‐bridgedcomplexes [Ti(L)(NPh)(py)]₂ ( 3 ), [Ti(L)(4‐F‐PhN)(py)]₂·Tol ( 4 ·Tol), [Ti(L)(4‐Cl‐PhN)(py)]₂·Tol·THF ( 5 ·Tol·THF), [Ti(L)(4‐Br‐PhN)(py)]₂·Tol ( 6 ·Tol) and a (bis)ligand‐coordinated complex Ti(L)₂·phen ( 7 ) (py = pyridine, phen = 1,10‐phenanthroline). Attempts to prepare the monomeric titianium imido complexes were unsuccessful. DFT studies show that the assumed compound which contains Ti = N species is less stable than imido‐bridged Ti‐N(R)‐Ti complexes, providing the better understanding of the experimental results.     

Solvent dependence of the solid‐state structures of salicylaldiminate magnesium amide complexes

There are challenges in using magnesium coordination complexes as reagents owing to their tendency to adopt varying aggregation states in solution and thus impacting the reactivity of the complexes. Many magnesium complexes are prone to ligand redistribution via Schlenk equilibrium due to the ionic character within the metal–ligand interactions. The role of the supporting ligand is often crucial for providing stability to the heteroleptic complex. Strategies to minimize ligand redistribution in alkaline earth metal complexes could include using a supporting ligand with tunable sterics and electronics to influence the degree of association to the metal atom. Magnesium bis(hexamethyldisilazide) was reacted with salicylaldimines [¹L = N‐(2,6‐diisopropylphenyl)salicylaldimine and ²L = 3,5‐di‐tert‐butyl‐N‐(2,6‐diisopropylphenyl)salicylaldimine] in either nondonor (toluene) or donor solvents [tetrahydrofuran (THF) or pyridine]. The structures of the magnesium complexes were studied in the solid state via X‐ray diffraction. In the nondonor solvent, i.e. toluene, the heteroleptic complex bis{μ‐2‐[(2,6‐diisopropylphenyl)iminomethyl]phenolato}‐κ³N,O:O;κ³O:N,O‐bis[(hexamethyldisilazido‐κN)magnesium(II)], [Mg₂(C₁₉H₂₂NO)₂(C₆H₁₈NSi₂)₂] or [¹LMgN(SiMe₃)₂]₂, (1), was favored, while in the donor solvent, i.e. pyridine (pyr), the formation of the homoleptic complex {2,4‐di‐tert‐butyl‐6‐[(2,6‐diisopropylphenyl)iminomethyl]phenolato‐κ²N,O}bis(pyridine‐κN)magnesium(II) toluene monosolvate, [Mg(C₂₇H₃₈NO)₂(C₅H₅N)₂]·C₅H₅N or [{²L₂Mg₂(pyr)₂}·pyr], (2), predominated. Heteroleptic complex (1) was crystallized from toluene, while homoleptic complexes (2) and the previously reported [¹L₂Mg·THF] [Quinque et al. (2011). Eur. J. Inorg. Chem. pp. 3321–3326] were crystallized from pyridine and THF, respectively. These studies support solvent‐dependent ligand redistribution in solution. In‐situ¹H NMR experiments were carried out to further probe the solution behavior of these systems.     

Synthesis of ferrocene‐containing N‐aryloxo β‐ketoiminate lanthanide complexes and polymerization of ε‐caprolactone

The synthesis, characterization and ε‐caprolactone polymerization behavior of lanthanide amido complexes stabilized by ferrocene‐containing N‐aryloxo functionalized β‐ketoiminate ligand FcCOCH₂C(Me)N(2‐HO‐5‐Bu^t‐C₆H₃) (LH₂, Fc = ferrocenyl) are described. The lanthanide amido complexes [LLnN(SiMe₃)₂(THF)]₂ [Ln = Nd ( 1 ), Sm ( 2 ), Yb ( 3 ), Y ( 4 )] were synthesized in good yields by the amine elimination reactions of LH₂ with Ln[N(SiMe₃)₂]₃(µ‐Cl)Li(THF)₃ in a 1:1 molar ratio in THF. These complexes were characterized by IR spectroscopy and elemental analysis, and ¹H NMR spectroscopy was added for the analysis of complex 4 . The definitive molecular structures of complexes 1 and 3 were determined by X‐ray diffraction studies. Complexes 1 – 4 can initiate the ring‐opening polymerization of ε‐caprolactone with moderate activity. Copyright © 2011 John Wiley & Sons, Ltd.     

Synthesis and Structural Characterization of Lanthanide Amides Stabilized by an N-Aryloxo Functionalized β-Ketoiminate Ligand

The synthesis and characterization of dimeric lanthanide amides stabilized by a dianionic N‐aryloxo functionalized β‐ketoiminate ligand are described in this paper. Reactions of 4‐(2‐hydroxy‐5‐tert‐butyl‐phenyl)imino‐2‐pentanone (LH₂) with Ln[N(SiMe₃)₂]₃(µ‐Cl)Li(THF)₃ in a 1:1 molar ratio in THF gave the dimeric lanthanide amido complexes [LLn{N(SiMe₃)₂}(THF)]₂ [Ln=Nd ( 1 ), Sm ( 2 ), Yb ( 3 ), Y ( 4 )] in good isolated yields. These complexes were characterized by IR spectroscopy, elemental analysis, and ¹H NMR spectroscopy in the case of complex 4 . The definitive molecular structures of complexes 1 , 3 , and 4 were determined. It was found that complexes 1 to 4 can initiate the ring‐opening polymerization of L‐lactide.     

Synthesis and Crystal Structure of [(1‐(Phenyltriazenido)‐2‐(phenyltriazeno)benzene)(nitrato)mercury(II)], {Hg[PhN3C6H4N3(H)Ph](NO3)}, a Complex with Weak Metal‐Arene π‐Interactions

The reaction of PhN₃(H)C₆H₄N₃(H)Ph with Hg(NO₃)₂ in THF in the presence of triethylamine yields {Hg[PhN₃C₆H₄N₃(H)Ph](NO₃)} as a yellow powder that can be recrystallized from THF/acetone. The crystals belong to the monoclinic system, space group P2₁ with the cell dimensions a = 9.639(2), b = 5.412(1), c = 19.675(4) Å, β= 97.47(3)°, V = 1017.7 (4) ų, Z = 2. The crystal structure determination (2668 unique reflections with [I>2σ(I)], 262 parameters, R₁ = 0.0393) shows that the structure consists of mononuclear complexes. Hg atoms are linearly coordinated by one N_α atom of the triazenide unit of the planar ligand [Hg‐N(1) = 2.101(8) Å] and an O atom of the NO₃^— ion [Hg‐O(1) = 2.11(1) Å]. Additional weak Hg‐N contacts [Hg‐N(4) = 2.662(9) and Hg‐N(3) = 2.851(9) Å] and an intramolecular hydrogen bond between the triazenide hydrogen and an O atom of the nitrate group are observed [N(6)‐H(6)···O(2) = 2.92(2) Å]. The complexes are stacked to infinite chains by metal‐arene π‐interactions. Each Hg atom is coordinated by the terminal phenyl rings of two neighboring complexes [Hg‐C from 3.40(1) to 4.10(1) Å] in a η² fashion.     

Chirale Gallium‐ und Indium‐Alkoxometallate

Chiral Gallium and Indium Alkoxometalates Li₂(S)‐BINOLate ((S)‐BINOL = (S)‐(–)‐2,2′‐Dihydroxy‐1,1′‐binaphthyl) generated by dilithiation of (S)BINOL with two equivalents ⁿBuLi was reacted with GaCl₃ und InCl₃ in THF to the alkoxometalates [{Li(THF)₂}{Li(THF)}₂{Ga((S)‐BINOLate)₃}] ( 1 ) and [{Li(THF)₂}₂{Li(THF)}{In((S)‐BINOLate)₃}] · [{Li(THF)₂}{Li(THF)}₂{In((S)‐ BINOLate)₃}]₂ ( 3 ), respectively. 1 and 3 crystallize from THF/toluene mixtures as 1 · 2 toluene and 3 · 8 toluene. The treatment of PhCH₂GaCl₂ with Li₂(S)‐BINOLate in THF under reflux, followed by recrystallization of the product from DME gives the gallate [{Li(DME)}₃{Ga((S)BINOLate)₃}] · 1.5 THF ( 2 · 1.5 THF). 1 – 3 were characterized by NMR, IR and MS techniques. In addition, 1 · 2 toluene, 2 · 1.5 THF and 3 · 8 toluene were investigated by X‐ray structure analyses. According to them, a distorted octahedral coordination sphere around the group 13 metal was formed, built‐up by three BINOLate ligands. The three Li⁺ counter ions act as bridging units by metal‐oxygen coordination. The coordination sphere of the Li⁺ ions was completed, depending on the available space, by one or two THF ligands ( 1 · 2 toluene, 3 · 8 toluene) and one DME ligand ( 2 · 1.5 THF), respectively. The sterical dominance of the BINOLate ligands can be shown by the almost square‐planar coordination of the Li⁺ ions in 2 · 1.5 THF giving a small twisting angle of only 17°.     

Synthesis,structure and in vitro antiproliferative activities of oxamido‐bridged dicopper(II) complexes: A comparative study of experimental evidence and molecular docking of DNA/protein binding

Two μ‐oxamido‐bridged dicopper(II) complexes, namely [Cu₂(hmpoxd)(H₂O)(phen)](ClO₄) ( 1 ) and [Cu₂(papo)(H₂O)(phen)](ClO₄)·2H₂O ( 2 ), where H₃hmpoxd and H₃papo represent N‐(2‐hydroxy‐5‐methylphenyl)‐N′‐[3‐(dimethylamino)propyl]oxamide and N‐(2‐hydroxylphenyl)‐N′‐(3‐aminopropyl)oxamide, respectively, and phen represents 1,10‐phenanthroline, were synthesized. Single‐crystal X‐ray crystallography and other methods revealed that the two copper(II) ions in complex 1 are bridged by the cis‐hmpoxd^3? with Cu···Cu separation of 5.1896(7) Å, in which the inner (Cu1) and outer (Cu2) copper(II) atoms are located in square‐planar and square‐pyramidal geometries, respectively. To evaluate the effects of bridging ligand hydrophobicity on DNA/protein binding and potential anticancer activities, comparative studies of the reactivity towards herring sperm DNA and protein bovine serum albumin (BSA) as well as cytotoxicity of complex 1 with our previously reported complex 2 were conducted theoretically and experimentally. The results indicate that the two complexes can interact interactively with DNA, and bind to BSA via the binding sites Trp213 for 1 and Trp134 for 2 . Interestingly, the in vitro anticancer activities and DNA/protein binding affinities consistently follow the order of 1 > 2 .     

Systematische Studie zu den Koordinationseigenschaften des Guanidin‐Liganden Bis(tetramethylguanidino)propan mit den Metallen Mangan,Cobalt, Nickel,Zink, Cadmium,Quecksilber und Silber

The transition metal complexes with the ligand 1,3‐bis(N,N,N′,N′‐tetramethylguanidino)propane (btmgp), [Mn(btmgp)Br₂] ( 1 ), [Co(btmgp)Cl₂] ( 2 ), [Ni(btmgp)I₂] ( 3 ), [Zn(btmgp)Cl₂] ( 4 ), [Zn(btmgp)(O₂CCH₃)₂] ( 5 ), [Cd(btmgp)Cl₂] ( 6 ), [Hg(btmgp)Cl₂] ( 7 ) and [Ag₂(btmgp)₂][ClO₄]₂·2MeCN ( 8 ), were prepared and characterised for the first time. The stoichiometric reaction of the corresponding water‐free metal salts with the ligand btmgp in dry MeCN or THF resulted in the straightforward formation of the mononuclear complexes 1 – 7 and the binuclear complex 8 . In complexes with M^II the metal ion shows a distorted tetrahedral coordination whereas in 8 , the coordination of the M^I ion is almost linear. The coordination behavior of btmgp and resulting structural parameters of the corresponding complexes were discussed in an comparative approach together with already described complexes of btmgp and the bisguanidine ligand N¹,N²‐bis(1,3‐dimethylimidazolidin‐2‐ylidene)‐ethane‐1,2‐diamine (DMEG₂e), respectively.     

Anion Effects on the Formation of Silver(I) Complexes with the Flexible Ligand 4,4′‐Bis(1,2,4‐triazol‐1‐ylmethyl)biphenyl

The reaction of 4,4′‐bis(1,2,4‐triazol‐1‐ylmethyl)biphenyl (btmb) with silver(I) salts of BF₄^–, NO₃^– and N₃^– led to the formation of four new silver(I) coordination polymers {[Ag(btmb)]BF₄}_n ( 1 ), {[Ag₂(btmb)₃](NO₃)₂(H₂O)₅}_n ( 2 ), [Ag₂(btmb)(N₃)₂]_n ( 3 ), and [Ag(btmb)(N₃)]_n ( 4 ). Their coordination number varies from 2 (in 1 ) to 3 (in 2 ), 4 (in 3 ), and 5 (in 4 ). Different from the single chain structure of 1 , complex 2 displays a 1D ladder‐like double chain framework, whereas complex 3 exhibits a 2D layered architecture. Complex 4 has the same anion as complex 3 but shows a different metal‐to‐ligand ratio and a 1D double‐zigzag chain structure. Both 3 and 4 have Ag ··· Ag argentophilic interactions. The ligand btmb adopts both cis or trans configuration in the studied complexes. A trans‐ or cis‐btmb ligand link silver ions with Ag ··· Ag distances of ≈?18 and 13 Å, respectively. BF₄^– and NO₃^– are non‐coordinating anions in 1 and 2 . N₃^– is the bridging anion in 3 (1,3‐bridging fashion) and 4 (1,1‐bridging fashion). These findings suggest that the coordination numbers around the Ag^I ion correlate to the coordination abilities of anions and the btmb to silver ratio. In addition, the influence of anions on thermal stability were also investigated. This work is a good example that nicely supports the less explored field of anion‐dependent structures of complexes with non‐pyridyl ligands.     

Lanthanide(II) Complexes of the Dihydrotriazinido Ligand [N{C(Ph)=N}2C(tBu)Ph]−

The potassium dihydrotriazinide K(L^Ph,tBu) ( 1 ) was obtained by a metal exchange route from [Li(L^Ph,tBu)(THF)₃] and KOtBu (L^Ph,tBu = [N{C(Ph)=N}₂C(tBu)Ph]). Reaction of 1 with 1 or 0.5 equivalents of SmI₂(thf)₂ yielded the monosubstituted Sm^II complex [Sm(L^Ph,tBu)I(THF)₄] ( 2 ) or the disubstituted [Sm(L^Ph,tBu)₂(THF)₂] ( 3 ), respectively. Attempted synthesis of a heteroleptic Sm^II amido‐alkyl complex by the reaction of 2 with KCH₂Ph produced compound 3 due to ligand redistribution. The Yb^II bis(dihydrotriazinide) [Yb(L^Ph,tBu)₂(THF)₂] ( 4 ) was isolated from the 1:1 reaction of YbI₂(THF)₂ and 1 . Molecular structures of the crystalline compounds 2 , 3· 2C₆H₆ and 4· PhMe were determined by X‐ray crystallography.