Synthesis and Characterization of Manganese(I) Carbonyl Complexes of the Type [(OC)4Mn{μ‐P(R)Aryl}]2

Metalation of secondary phosphanes HPRR′ [R = R′ = C₆H₄‐4‐Me, C₆H₃‐3,5‐Me₂ ( 3 ), C₆H₄‐4‐NMe₂ ( 4 ); R/R′ = Ph/cHex] with Mn₂(CO)₁₀ in boiling xylene (mixture of isomers), until the evolution of gaseous carbon monoxide ceases, leads to the formation of the dinuclear complexes of the type [(OC)₄Mn(μ‐PRR′)]₂ [R = R′ = C₆H₄‐4‐Me ( 5 ), C₆H₃‐3,5‐Me₂ ( 6 ), R/R′ = Ph/cHex ( 7 ), R = R′ = C₆H₄‐4‐NMe₂ ( 8 )] with poor to moderate yields. These manganese(I) complexes are only sparingly soluble or even nearly insoluble in hydrocarbons at room temperature. Planar four‐membered Mn₂P₂ rings represent the central moiety with four carbonyl ligands at each manganese(I) atom. The steric demand of the P‐bound substituents influences the Mn–P bond lengths as well as the P–Mn–P bond angles.     

Discrete Magnesium Hydride Aggregates: A Cationic Mg13H18 Cluster Stabilized by NNNN‐Type Macrocycles

Large magnesium hydride aggregates [Mg₁₃(Me₃TACD)₆(μ₂‐H₁₂)(μ₃‐H₆)][A]₂ ((Me₃TACD)H=1,4,7‐trimethyl‐1,4,7,10‐tetraazacyclododecane; A=AlEt₄, AlnBu₄, B{3,5‐(CF₃)₂C₆H₃}₄) were synthesized stepwise from alkyl complexes [Mg₂(Me₃TACD)R₃] (R=Et, nBu) and phenylsilane in the presence of additional Mg^II ions. The central magnesium atom is octahedrally coordinated by six hydrides as in solid α‐MgH₂ of the rutile type. Further coordination to six magnesium atoms leads to a substructure of seven edge‐sharing octahedra as found in the hexagonal layer of brucite (Mg(OH)₂). Upon protonolysis in the presence of 1,2‐dimethoxyethane (DME), this cluster was degraded into a tetranuclear dication [Mg₂(Me₃TACD)(μ‐H)₂(DME)]₂[A]₂.     

Synthesis and characterization of heterobimetallic mixed-ligand complexes containing Zr(μ-OPri)2Al bridging units

Interesting varieties of heterobimetallic mixed-ligand complexes [Zr{M(OPrⁱ) _n }₂ (L)] (where M = Al, n = 4, L = OC₆H₄CH = NCH₂CH₂O (1); M = Nb, n = 6, L = OC₆H₄CH = NCH₂CH₂O (2); M = Al, n = 4, L = OC₁₀H₆CH = NCH₂CH₂O (3); M = Nb, n = 6, L = OC₁₀H₆CH = NCH₂CH₂O (4)), [Zr{Al(OPrⁱ)₄}₂Cl(OAr)] (where Ar = C₆H₃Me₂-2,5 (5); Ar = C₆H₂Me-4-Bu₂-2,6 (6), [Zr{Al(OPrⁱ)₄}₂(OAr)₂] (where Ar = C₆H₃Me₂-2,5 (7); Ar = C₆H₂Me-4-Bu₂-2,6 (8), [Zr{Al(OPrⁱ)₄}₃(OAr)] (where Ar = C₆H₃Me₂-2,5 (9); Ar = C₆H₃Me₂-2,6 (10), [ZrAl(OPrⁱ)_7-n (ON=CMe₂) _n ] (where n = 4 (11); n = 7 (12), [ZrAl₂(OPrⁱ)_10-n (ON=CMe₂) _n ] (where n = 4 (13); n = 6 (14); n = 10 (15) and [Zr{Al(OPrⁱ)₄}₂{ON=CMe(R)} _n Cl_2–n] [where n = 1, R = Me (16); n = 2, R = Me (17); n = 1, R = Et (18); n = 2, R = Et (19)] have been prepared either by the salt elimination method or by alkoxide-ligand exchange. All of these heterobimetallic complexes have been characterized by elemental analyses, molecular weight measurements, and spectroscopic (I.r., ¹H-, and ²⁷Al- n.m.r.) studies.     

Synthesis and Utility of Neptunium(III) Hydrocarbyl Complex

To extend organoactinide chemistry beyond uranium, reported here is the first structurally characterized transuranic hydrocarbyl complex, Np[η⁴‐Me₂NC(H)C₆H₅]₃ ( 1 ), from reaction of NpCl₄(DME)₂ with four equivalents of K[Me₂NC(H)C₆H₅]. Unlike the U^III species, the neptunium analogue can be used to access other Np^III complexes. The reaction of 1 with three equivalents of HE₂C(2,6‐Mes₂‐C₆H₃) (E=O, S) yields [(2,6‐Mes₂‐C₆H₃)CE₂]₃Np(THF)₂, maintaining the trivalent oxidation state.     

Synthesis,Structures, and Properties of Four Novel Coordination Compounds based on a Flexible Tetrakis(imidazol‐1‐ylmethyl)methane Ligand

Four coordination polymers, namely, [Zn₂(TIYM)(2,6‐PYDC)₂]_n · n(CH₃OH) · 3n(H₂O) ( 1 ), [Cu(TIYM)(2,6‐PYDC)]_n · 3n(H₂O) ( 2 ), [Co(TIYM)(2,6‐PYDC)]_n · n(CH₃OH) · 3n(H₂O) ( 3 ), and [Cd₂(TIYM)(2,6‐PYDC)₂(H₂O)]_n · n(H₂O) ( 4 ) with the flexible N‐containing ligand [tetrakis(imidazol‐1‐ylmethyl)methane (TIYM)] and the N‐containing dicarboxylic acid [2,6‐pyridinedicarboxylic acid (2,6‐PYDC)] were prepared. Compounds 1 – 4 show various structures because of different N–C_center–N angles (θ) of TIYM ligands and changing coordination modes of 2,6‐PYDC. Compounds 1 , 2 , and 3 display a similar 1D ladder‐like chain, whereas 4 gives a 1D quad‐core lifting platform shaped belt. The structural diversities in 1 – 4 suggest that the multiple coordination modes or the different freely twist angles of ligands and the presence of different metal atoms play important roles in the resulting structures of the coordination polymers. Furthermore, the solid‐state luminescence properties of 1 and 4 , and the magnetic properties of 3 were investigated.     

Bimetallic Rare Earth Alkyl Complexes Bearing Bridged Amidinate Ligands: Synthesis and Activity for L-Lactide Polymerization

Four novel bridged‐amidines H₂L {1,4‐R¹[C(=NR²)(NHR²)]₂ [R¹=C₆H₄, R²=2,6‐ⁱPr₂C₆H₃ (H₂L¹); R¹=C₆H₄, R²=2,6‐Me₂C₆H₃ (H₂L²); R¹=C₆H₁₀, R²=2,6‐ⁱPr₂C₆H₃ (H₂L³); R¹=C₆H₁₀, R²=2,6‐Me₂C₆H₃ (H₂L⁴)]} were synthesized in 65%–78% isolated yields by the condensation reaction of dicarboxylic acid with four equimolar amounts of amines in the presence of PPSE at 180°C. Alkane elimination reaction of Ln(CH₂SiMe₃)₃(THF)₂ (Ln=Y, Lu) with 0.5 equiv. of amidine in THF at room temperature afforded the corresponding bimetallic rare earth alkyl complexes (THF)(Me₃SiCH₂)₂LnL¹Ln(CH₂SiMe₃)₂(THF) [Ln=Y ( 1 ), Lu ( 2 )], (THF)(Me₃SiCH₂)₂LnL²Ln‐ (CH₂SiMe₃)₂(THF) [Ln=Y ( 3 ), Lu ( 4 )], (THF)(Me₃SiCH₂)₂YL³Y(CH₂SiMe₃)₂(THF) ( 5 ), (THF)(Me₃SiCH₂)₂YL⁴‐ Y(CH₂SiMe₃)₂(THF) ( 6 ) in 72% –80% isolated yields. These neutral complexes showed activity towards L‐lactide polymerization in toluene at 70°C to give high molecular weight (M>10⁴) and narrow molecular weight distribution (M_w/M_n≦1.40) polymers     

Reactivity of an N,N‐Chelated Germylene Toward Substituted Alkynes,Alkenes, and Allenes

Treatment of N,N‐chelated germylene [(iPr)₂NB(N‐2,6‐Me₂C₆H₃)₂]Ge ( 1 ) with ferrocenyl alkynes containing carbonyl functionalities, FcC≡CC(O)R, resulted in [2+2+2] cyclization and formation of the respective ferrocenylated 3‐Fc‐4‐C(O)R‐1,2‐digermacyclobut‐3‐enes 2 – 4 [R = Me ( 2 ), OEt ( 3 ) and NMe₂ ( 4 )] bearing intact carbonyl substituents. In contrast, the reaction between 1 and PhC(O)C≡CC(O)Ph led to activation of both C≡C and C=O bonds producing bicyclic compound containing two five‐membered 1‐germa‐2‐oxacyclopent‐3‐ene rings sharing one C–C bond, 4,8‐diphenyl‐3,7‐dioxa‐2,6‐digermabicyclo[3.3.0]octa‐4,8‐diene ( 5 ). With N‐methylmaleimide containing an analogous C(O)CH=CHC(O) fragment, germylene 1 reacted under [2+2+2] cyclization involving the C=C double bond, producing 1,2‐digermacyclobutane 6 with unchanged carbonyl moieties. Finally, 1 selectively added to the terminal double bond in allenes CH₂=C=CRR′ giving rise to 3‐(=CRR′)‐1,2‐digermacyclobutanes [R/R′ = Me/Me ( 7 ), H/OMe ( 8 )] bearing an exo‐C=C double bond. All compounds were characterized by ¹H, ¹³C{¹H} NMR, IR and Raman spectroscopy and the molecular structures of 3 , 4 , 5 , and 8 were established by single‐crystal X‐ray diffraction analysis. The redox behavior of ferrocenylated derivatives 2 – 4 was studied by cyclic voltammetry.     

The Effect of Hard and Soft Donors on Structural Motifs in (Isocyanide)gold(I) Complexes

Treatment of the (isocyanide)gold(I) species LAuCl (L=^tBuNC, 2,6‐Me₂C₆H₃NC) with 4‐mercaptobenzoic acid in the presence of NaOMe yields the complexes [Au(4‐SC₆H₄CO₂H)L] in good yield. Reaction of LAuCl with 2‐HSQn (Qn=quinoline) and 2‐HSPy (Py=pyridine) under the same conditions provides the thiolato compounds [Au(2‐SQn)L] and [Au(2‐SPy)L], respectively. A structural investigation of the pyridylthiolato compound revealed chains of molecules with alternating medium and long Au−Au interactions. Treatment of this compound with HBF₄ results in the cationic species [Au(2‐HSPy)(2,6‐Me₂C₆H₃NC)]⁺ as the BF₄⁻ salt. The same product is obtained on reaction of [AuCl(2,6‐Me₂C₆H₃NC)] with AgOTf followed by HSPy. Treatment of the gold(I) halide compounds LAuCl (L=^tBuNC, 2,6‐Me₂C₆H₃NC) with potassium 1,3,4‐thiadiazole‐2,5‐dithiolate (KSSSK) leads to the isolation of dinuclear thiolatogold complexes [(AuL)₂(SSS)]. These products go on to form insoluble polymers through loss of isocyanide on standing in solution. A single crystal of [{Au(^tBuNC)}₂(SSS)] was obtained and the subsequent structural analysis revealed one of the most complicated networks known based solely on aurophilic interactions. A good comparison to the ‘soft' S‐donation of the thiolato ligands was provided by the synthesis of a number of nitratogold(I)complexes with the anion bound through the ‘hard' O‐donor. Reaction of ⁱPrNC and CyNC with Au(tht)Cl provided the complexes [AuCl(ⁱPrNC)] and [AuCl(CyNC)], respectively. These compounds were found to yield the respective nitrato species [Au(NO₃)ⁱPrNC)] and [(Au(NO₃)(CyNC)] on treatment with AgNO₃. The nitrato complexes yielded single crystals enabling a structural investigation to be carried out. While [Au(NO₃)(CyNC)] has a more conventional structure with dimers aligned into strings with alternating short and long aurophilic bonding, [Au(NO₃)(ⁱPrNC)] has a unique structure based on strings of alternating, corner‐sharing Au₆ and Au₈ units with short Au−Au contacts in edge‐sharing Au₃ triangles.     

Molecular weight control of polyethylene waxes using a constrained imino‐cyclopenta[b]pyridyl‐nickel catalyst

Five examples of nickel(II) bromide complexes bearing N,N‐imino‐cyclopenta[b ]pyridines, [7‐(ArN)‐6,6‐Me₂C₈H₅N]NiBr₂ (Ar = 2,6‐Me₂C₆H₃ ( Ni1 ), 2,6‐Et₂C₆H₃ ( Ni2 ), 2,6‐i‐ Pr₂C₆H₃ ( Ni3 ), 2,4,6‐Me₃C₆H₂ ( Ni4 ), 2,6‐Et₂‐4‐MeC₆H₂ ( Ni5 )), have been prepared by the reaction of the corresponding ligand, L1 – L5 , with NiBr₂(DME) (DME = 1,2‐dimethoxyethane). On crystallization from bench dichloromethane, Ni1 underwent adventitious reaction with water to give the aqua salt, [ L1 NiBr(OH₂)₃][Br] ( Ni1' ). The molecular structures of Ni1' and Ni3 have been structurally characterized, the latter revealing a bromide‐bridged dimer. On activation with either MMAO or Et₂AlCl, Ni1 , Ni2 , Ni4, and Ni5 , all exhibited high activities for ethylene polymerization (up to 3.88 × 10⁶ g(PE) mol^?1(Ni) h^?1); the most sterically bulky Ni3 gave only low activity. Polyethylene waxes are a feature of the materials obtained which typically display low molecular weights (M _ws), narrow M _w distributions and unsaturated vinyl and vinylene functionalities. Notably, the catalyst comprising Ni1 /Et₂AlCl produced polyethylene with the lowest M _w, 0.67 kg mol^?1, which is less than any previously reported data for any class of cycloalkyl‐fused pyridine–nickel catalyst. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55 , 3494–3505     

Direct Synthesis of Titanium Complexes with Chelating cis‐9,10‐Dihydrophenanthrenediamide Ligands through Sequential C?C Bond‐Forming Reactions from o‐Metalated Arylimines

A series of new titanium(IV) complexes with o‐metalated arylimine and/or cis‐9,10‐dihydrophenanthrenediamide ligands, [o‐C₆H₄(CH?NR)TiCl₃] (R=2,6‐iPr₂C₆H₃ ( 3 a ), 2,6‐Me₂C₆H₃ ( 3 b ), tBu ( 3 c )), [cis‐9,10‐PhenH₂(NR)₂TiCl₂] (PhenH₂=9,10‐dihydrophenanthrene; R=2,6‐iPr₂C₆H₃ ( 4 a ), 2,6‐Me₂C₆H₃ ( 4 b ), tBu ( 4 c )), [{cis‐9,10‐PhenH₂(NR)₂}{o‐C₆H₄(HC?NR)}TiCl] (R=2,6‐iPr₂C₆H₃ ( 5 a ), 2,6‐Me₂C₆H₃ ( 5 b ), tBu ( 5 c )), have been synthesised from the reactions of TiCl₄ with o‐C₆H₄(CH?NR)Li (R=2,6‐iPr₂C₆H₃, 2,6‐Me₂C₆H₃, tBu). Complexes 4 and 5 were formed unexpectedly from the reactions of TiCl₄ with two or three equivalents of the corresponding o‐C₆H₄(CH?NR)Li followed by sequential intramolecular C? C bond‐forming reductive elimination and oxidative coupling reactions. Attempts to isolate the intermediates, [{o‐C₆H₄(CH?NR)}₂TiCl₂] ( 2 ), were unsuccessful. All complexes were characterised by ¹H and ¹³C NMR spectroscopy, and the molecular structures of 3 a , 4 a – c , 5 a , and 5 c were determined by X‐ray crystallography.     

Metallorganische Verbindungen der Lanthanoide. 88. Monomere Lanthanoid(III)-amide: Synthese und Röntgenstrukturanalyse von [Nd{N(C6H5)(SiMe3)}3(THF)], [Li(THF)2(μ-Cl)2Nd{N(C6H3Me2-2,6)(SiMe3)}2(THF)] und [ClNd{N(C6H3-iso-Pr2-2,6)(SiMe3)}2(THF)]

Organometallic Compounds of the Lanthanides. 88. Monomeric Lanthanide(III) Amides: Synthesis and X-Ray Crystal Structure of [Nd{N(C₆H₅)(SiMe₃)}₃(THF)], [Li(THF)₂(μ-Cl)₂Nd{N(C₆H₃Me₂-2,6)(SiMe₃)}₂(THF)], and [ClNd{N(C₆H₃-iso-Pr₂-2,6)(SiMe₃)} ₂(THF)] A series of lanthanide(III) amides [Ln{N(C₆H₅) · (SiMe₃)}₃(THF)_x] [Ln = Y ( 1 ), La ( 2 ), Nd ( 3 ), Sm ( 4 ), Eu ( 5 ), Tb ( 6 ), Er ( 8 ), Yb ( 9 ), Lu ( 10 )] could be prepared by the reaction of lanthanide trichlorides, LnCl₃, with LiN(C₆H₅)(SiMe₃). Treatment of NdCl₃(THF)₂ and LuCl₃(THF)₃ with the lithium salts of the bulky amides [N(C₆H₃R₂-2,6)(SiMe₃)]^? (R = Me, iso-Pr) results in the formation of the lanthanide diamides [Li(THF)₂(μ-Cl)₂Nd{N(C₆H₃Me₂-2, 6)(SiMe₃)}₂(THF)] ( 11 ) and [ClLn{N(C₆H₃-iso-Pr₂-2,6)(SiMe₃)} ₂(THF)] [Ln = Nd ( 12 ), Lu ( 13 )], respectively. The ¹H- and ¹³C-NMR and mass spectra of the new compounds as well as the X-ray crystal structures of the neodymium derivatives 3 , 11 and 12 are discussed.     

Light‐Induced Rearrangement of Thioether‐Substituted Phosphanide Ligands: Scope and Limitations of a Remarkable Isomerization

Treatment of the thioether‐substituted secondary phosphanes R²PH(C₆H₄‐2‐SR¹) [R²=(Me₃Si)₂CH, R¹=Me ( 1_PH ), iPr ( 2_PH ), Ph ( 3_PH ); R²=tBu, R¹=Me ( 4_PH ); R²=Ph, R¹=Me ( 5_PH )] with nBuLi yields the corresponding lithium phosphanides, which were isolated as their THF ( 1 – 5_Pa ) and tmeda ( 1 – 5_Pb ) adducts. Solid‐state structures were obtained for the adducts [R²P(C₆H₄‐2‐SR¹)]Li(L)_n [R²=(Me₃Si)₂CH, R¹=nPr, (L)_n=tmeda ( 2_Pb ); R²=(Me₃Si)₂CH, R¹=Ph, (L)_n=tmeda ( 3_Pb ); R²=Ph, R¹=Me, (L)_n=(THF)_1.33 ( 5_Pa ); R²=Ph, R¹=Me, (L)_n=([12]crown‐4)₂ ( 5_Pc )]. Treatment of 1_PH with either PhCH₂Na or PhCH₂K yields the heavier alkali metal complexes [{(Me₃Si)₂CH}P(C₆H₄‐2‐SMe)]M(THF)_n [M=Na ( 1_Pd ), K ( 1_Pe )]. With the exception of 2_Pa and 2_Pb , photolysis of these complexes with white light proceeds rapidly to give the thiolate species [R²P(R¹)(C₆H₄‐2‐S)]M(L)_n [M=Li, L=THF ( 1_Sa , 3_Sa – 5_Sa ); M=Li, L=tmeda ( 1_Sb , 3_Sb – 5_Sb ); M=Na, L=THF ( 1_Sd ); M=K, L=THF ( 1_Se )] as the sole products. The compounds 3_Sa and 4_Sa may be desolvated to give the cyclic oligomers [[{(Me₃Si)₂CH}P(Ph)(C₆H₄‐2‐S)]Li]₆ (( 3_S )₆) and [[tBuP(Me)(C₆H₄‐2‐S)]Li]₈ (( 4_S )₈), respectively. A mechanistic study reveals that the phosphanide–thiolate rearrangement proceeds by intramolecular nucleophilic attack of the phosphanide center at the carbon atom of the substituent at sulfur. For 2_Pa / 2_Pb , competing intramolecular β‐deprotonation of the n‐propyl substituent results in the elimination of propene and the formation of the phosphanide–thiolate dianion [{(Me₃Si)₂CH}P(C₆H₄‐2‐S)]^2?.     

Stable N‐Heterocyclic Carbene Adducts of Arylchlorosilylenes and Their Germanium Homologues

The first N‐heterocyclic carbene adducts of arylchlorosilylenes are reported and compared with the homologous germanium compounds. The arylsilicon(II) chlorides SiArCl(Im‐Me₄) [Ar=C₆H₃‐2,6‐Mes₂ (Mes=C₆H₂‐2,4,6‐Me₃), C₆H₃‐2,6‐Trip₂ (Trip=C₆H₂‐2,4,6‐iPr₃)] were obtained selectively on dehydrochlorination of the arylchlorosilanes SiArHCl₂ with 1,3,4,5‐tetramethylimidazol‐2‐ylidene (Im‐Me₄). The analogous arylgermanium(II) chlorides GeArCl(Im‐Me₄) were prepared by metathetical exchange of GeCl₂(Im‐Me₄) with LiC₆H₃‐2,6‐Mes₂ or addition of Im‐Me₄ to GeCl(C₆H₃‐2,6‐Trip₂). All compounds were fully characterized. Density functional calculations on ECl(C₆H₃‐2,6‐Trip₂)(Im‐Me₄), where E=Si, Ge, at different levels of theory show very good agreement between calculated and experimental bonding parameters, and NBO analyses reveal similar electronic structures of the two aryltetrel(II) chlorides. The low gas‐phase Gibbs free energy of bond dissociation of SiCl(C₆H₃‐2,6‐Trip₂)(Im‐Me₄) (Δ${G{{{\circ}\hfill \atop {\rm calcd}\hfill}}}$ =28.1 kJ mol^?1) suggests that the carbene adducts SiArCl(Im‐Me₄) may be valuable transfer reagents of the arylsilicon(II) chlorides SiArCl.     

Reversible Cleavage/Formation of the Chromium–Chromium Quintuple Bond in the Highly Regioselective Alkyne Cyclotrimerization

Herein we report the employment of the quintuply bonded dichromium amidinates [Cr{κ²‐HC(N‐2,6‐ⁱPr₂C₆H₃)(N‐2,6‐R₂C₆H₃)}]₂ (R=iPr ( 1 ), Me ( 7 )) as catalysts to mediate the [2+2+2] cyclotrimerization of terminal alkynes giving 1,3,5‐trisubstituted benzenes. During the catalysis, the ultrashort Cr−Cr quintuple bond underwent reversible cleavage/formation, corroborated by the characterization of two inverted arene sandwich dichromium complexes (μ‐η⁶:η⁶‐1,3,5‐(Me₃Si)₃C₆H₃)[Cr{κ²‐HC(N ‐2,6‐ⁱPr₂C₆H₃)(N ‐2,6‐R₂C₆H₃)}]₂ (R=ⁱPr ( 5 ), Me ( 8 )). In the presence of σ donors, such as THF and 2,4,6‐Me₃C₆H₂CN, the bridging arene 1,3,5‐(Me₃Si)₃C₆H₃ in 5 and 8 was extruded and 1 and 7 were regenerated. Theoretical calculations were employed to disclose the reaction pathways of these highly regioselective [2+2+2] cylcotrimerization reactions of terminal alkynes.     

Zur Reaktivität von Titanocenkomplexen [Ti(Cp′)2(η2‐Me3SiC≡CSiMe3)] (Cp′ = Cp,Cp*) gegenüber Benzoldicarbonsäuren

On the Reactivity of Titanocene Complexes [Ti(Cp′)₂(η²‐Me₃SiC≡CSiMe₃)] (Cp′ = Cp, Cp*) towards Benzenedicarboxylic Acids Titanocene complexes [Ti(Cp′)₂(BTMSA)] ( 1a , Cp′ = Cp = η⁵‐C₅H₅; 1b , Cp′ = Cp* = η⁵‐C₅Me₅; BTMSA = Me₃SiC≡CSiMe₃) were found to react with iodine and methyl iodide yielding [Ti(Cp′)₂(μ‐I)₂] ( 2a / b ; a refers to Cp′ = Cp and b to Cp′ = Cp*), [Ti(Cp′)₂I₂] ( 3a / b ) and [Ti(Cp′)₂(Me)I] ( 4a / b ), respectively. In contrast to 2a , complex 2b proved to be highly moisture sensitive yielding with cleavage of HCp* [{Ti(Cp*)I}₂(μ‐O)] ( 7 ). The corresponding reactions of 1a / b with p‐cresol and thiophenol resulted in the formation of [Ti(Cp′)₂{O(p‐Tol)}₂] ( 5a / b ) and [Ti(Cp′)₂(SPh)₂] ( 6a / b ), respectively. Reactions of 1a and 1b with 1,n‐benzenedicarboxylic acids (n = 2–4) resulted in the formation of dinuclear titanium(III) complexes of the type [{Ti(Cp′)₂}₂{μ‐1,n‐(O₂C)₂C₆H₄}] (n = 2, 8a / b ; n = 3, 9a / b ; n = 4, 10a / b ). All complexes were fully characterized analytically and spectroscopically. Furthermore, complexes 7 , 8b , 9a ·THF, 10a / b were also be characterized by single‐crystal X‐ray diffraction analyses.     

Factors affecting product distributions in ethylene/styrene copolymerization by (aryloxo)(cyclopentadienyl)titanium complexes‐MAO catalyst systems

Ethylene/styrene copolymerizations using Cp′TiCl₂(O‐2,6‐ⁱPr₂C₆H₃) [Cp′ = Cp* (C₅Me₅, 1 ), 1,2,4‐Me₃C₅H₂ ( 2 ), tert‐BuC₅H₄ ( 3 )]‐MAO catalyst systems were explored under various conditions. Complexes 2 and 3 exhibited both high catalytic activities (activity: 504–6810 kg‐polymer/mol‐Ti h) and efficient styrene incorporations at 25, 40°C (ethylene 6 atm), affording relatively high molecular weight poly (ethylene‐co‐styrene)s with unimodal molecular weight distributions as well as with uniform styrene distributions (M_w = 6.12–13.6 × 10⁴, M_w/M_n = 1.50–1.71, styrene 31.7–51.9 mol %). By‐productions of syndiotactic polystyrene (SPS) were observed, when the copolymerizations by 1 – 3 ‐MAO catalyst systems were performed at 55, 70 °C (ethylene 6 atm, SPS 9.0–68.9 wt %); the ratios of the copolymer/SPS were affected by the polymerization temperature, the [styrene]/[ethylene] feed molar ratios in the reaction mixture, and by both the cyclopentadienyl fragment (Cp′) and anionic ancillary donor ligand (L) in Cp′TiCl₂(L) (L = Cl, O‐2,6‐ⁱPr₂C₆H₃ or N=C^tBu₂) employed. Co‐presence of the catalytically‐active species for both the copolymerization and the homopolymerization was thus suggested even in the presence of ethylene; the ratios were influenced by various factors (catalyst precursors, temperature, styrene/ethylene feed molar ratio, etc.). © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 4162–4174, 2008     

Chromium to chromium quintuple bonds in a trigonal lantern configuration

A new family of the quintuply bonded dichromium complexes [Cr₂{μ‐κ²‐HC(N‐2,6‐R₂C₆H₃)₂}₂(μ‐κ²‐HC[NAr]₂)] (R = ⁱPr, Ar = 4‐MeC₆H₄ ( 5 ), Ar = 3,5‐Me₂C₆H₃ ( 6 ), and Ar = 2,6‐Me₂C₆H₃ ( 7 ); R = Et, Ar = 4‐MeC₆H₄ ( 8 ), Ar = 3,5‐Me₂C₆H₃ [ 9 ], and Ar = 2,6‐Et₂C₆H₃ ( 10 )) with a heteroleptic lantern configuration was obtained upon the addition of one equivalent of amidinate to the quintuply bonded dichromium amidinates [Cr{μ‐κ²‐HC(N‐2,6‐R₂C₆H₃)₂}]₂ (R = ⁱPr, Et). Additionally, the same approach was applied to the preparation of the acetate derivative [Cr₂{μ‐κ²‐HC(N‐2,6‐ ⁱPr₂C₆H₃)₂}₂(μ‐κ²‐CH₃CO₂)] ( 11 ), which represents the first example that the quintuply bonded dinuclear complex contains an oxygen‐containing ligand. Of particular interest is that the Cr‐Cr bond lengths in these new trigonal paddlewheel quintuple Cr‐Cr bond species are comparable with those in their precursor compounds. They show ultrashort Cr‐Cr bond lengths in a narrow range of 1.740–1.755 å on the basis of single‐crystal X‐ray crystallography. The small Mayer bond orders of the long Cr‐N bonds as well as divergent, C_2v and D_3h, structural conformations in 5 – 11 suggest that the metal–ligand interactions possess minor covalent character and the electrostatic interactions play a dominant role. As a result, these extremely short Cr‐Cr quintuple bonds are caused by the overlap between five pairs of d orbitals that do not involve much in metal–ligand bonding. Additionally, anionic lantern dichromium trisamidinates 5 – 10 can be chemically oxidized by one electron, supported by electrochemistry, and their ease to undergo oxidation is presumably associated with their neutral lantern dichromium trisamindinate products, whose structures inherently display a Jahn‐Teller distortion, exemplified by the structure of the homoleptic dichromium complex [Cr₂{μ‐κ²‐HC(N‐2,6‐Et₂C₆H₃)₂}₃] [ 12 ] determined by X‐ray crystallography. These results unambiguously support the Cr‐Cr quintuple bonding in these novel anionic lantern dichromium complexes.     

New Polydentate Trimethylsilyl Chalcogenide Reagents for the Assembly of Polyferrocenyl Architectures

A series of polychalcogenotrimethylsilane complexes Ar(CH₂ESiMe₃)_n, (Ar=aryl; E=S, Se; n=2, 3, and 4) can be prepared from the corresponding polyorganobromide and M[ESiMe₃] (M=Na, Li). These represent the first examples of the incorporation of such a large number of reactive ?ESiMe₃ moieties onto an organic molecular framework. They are shown to be convenient reagents for the preparation of the polyferrocenylseleno‐ and thioesters from ferrocenoyl chloride. The synthesis, structures, and spectroscopic properties of the new silyl chalcogen complexes 1,4‐(Me₃SiECH₂)₂(C₆Me₄) (E=S, 1 ; E=Se, 2 ), 1,3,5‐(Me₃SiECH₂)₃(C₆Me₃) (E=S, 3 ; E=Se, 4 ) and 1,2,4,5‐(Me₃SiECH₂)₄(C₆H₂) (E=S, 5 ; E=Se, 6 ) and the polyferrocenyl chalcogenoesters [1,4‐{FcC(O)ECH₂}₂(C₆Me₄)] (E=S, 7 ; E=Se, 8 ), [1,3,5‐{FcC(O)ECH₂}₃(C₆Me₃)] (E=S, 9 ; E=Se, 10 ) and [1,2,4,5‐{FcC(O)ECH₂}₄(C₆H₂)] (E=S, 11 illustrated; E=Se, 12 ) are reported. The new polysilylated reagents and polyferrocenyl chalcogenoesters have been characterized by multinuclear NMR spectroscopy (¹H, ¹³C, ⁷⁷Se), electrospray ionization mass spectrometry and, for complexes 1 , 2 , 3 , 4 , 7 , 8 , and 11 , single‐crystal X‐ray diffraction. The cyclic voltammograms of complexes 7 – 11 are presented.     

Syntheses,Structures, and Photoluminescence of Lanthanide Coordination Polymers Based on 4‐Oxo‐1,4‐dihydro‐2,6‐pyridinedicarboxylic acid

Investigating the coordination chemistry of H₂CDA (4‐oxo‐1,4‐dihydro‐2,6‐pyridinedicarboxylic acid) with rare earth salts Ln(NO₃)₃ under hydrothermal conditions, structure transformation phenomenon was observed. The ligand, H₂CDA charged to its position isomer, enol type structure, H₃CAM (4‐hydroxypyridine‐2,6‐dicarboxylic acid). Six new lanthanide(III) coordination polymers with the formulas [Ln(CAM)(H₂O)₃]_n [Ln = La ( 1 ), Pr, ( 2 )] and {[Ln(CAM)(H₂O)₃] · H₂O}_n [Ln = Nd, ( 3 ), Sm, ( 4 ), Eu, ( 5 ), Y, ( 6 )] were synthesized and characterized. The X‐ray structure analyses show two kinds of coordination structures. The complexes 1 and 2 and 3 – 6 are isostructural. Complexes 1 and 2 crystallize in the monoclinic C₂/c space group, whereas 3 – 6 crystallize in the monoclinic system with space group P2₁/n. In the two kinds of structures, H₃CAM displays two different coordination modes. The Sm^III and Eu^III complexes exhibit the corresponding characteristic luminescence in the visible region at an excitation of 376 nm.     

Olefin polymerization and copolymerization with soluble transition‐metal complex catalysts

Olefin polymerizations catalyzed by Cp′TiCl₂(O‐2,6‐ⁱPr₂C₆H₃) ( 1 – 5 ; Cp′ = cyclopentadienyl group), RuCl₂(ethylene)(pybox) { 7 ; pybox = 2,6‐bis[(4S)‐4‐isopropyl‐2‐oxazolin‐2‐yl]pyridine}, and FeCl₂(pybox) ( 8 ) were investigated in the presence of a cocatalyst. The Cp*TiCl₂(O‐2,6‐ⁱPr₂C₆H₃) ( 5 )–methylaluminoxane (MAO) catalyst exhibited remarkable catalytic activity for both ethylene and 1‐hexene polymerizations, and the effect of the substituents on the cyclopentadienyl group was an important factor for the catalytic activity. A high level of 1‐hexene incorporation and a lower r_E · r_H value with 5 than with [Me₂Si(C₅Me₄)(N^tBu)]TiCl₂ ( 6 ) were obtained, despite the rather wide bond angle of Cp Ti O (120.5°) of 5 compared with the bond angle of Cp Ti N of 6 (107.6°). The 7 –MAO catalyst exhibited moderate catalytic activity for ethylene homopolymerization and ethylene/1‐hexene copolymerization, and the resultant copolymer incorporated 1‐hexene. The 8 –MAO catalyst also exhibited activity for ethylene polymerization, and an attempted ethylene/1‐hexene copolymerization gave linear polyethylene. The efficient polymerization of a norbornene macromonomer bearing a ring‐opened poly(norbornene) substituent was accomplished by ringopening metathesis polymerization with the well‐defined Mo(CHCMe₂Ph)(N‐2,6‐ⁱPr₂C₆H₃)[OCMe(CF₃)₂]₂ ( 10 ). The key step for the macromonomer synthesis was the exclusive end‐capping of the ring‐opened poly(norbornene) with p‐Me₃SiOC₆H₄CHO, and the use of 10 was effective for this polymerization proceeding with complete conversion. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 4613–4626, 2000