Polypropylene and poly(ethylene‐co‐1‐octene) effective synthesis with diamine‐bis(phenolate) complexes: Effect of complex structure on catalyst activity and product microstructure

A series of group 4 metal complexes bearing amine‐bis(phenolate) ligands with the amino side‐arm donor: (μ‐O)[Me₂N(CH₂)₂N(CH₂‐2‐O‐3,5‐tBu₂‐C₆H₂)₂ZrCl]₂ ( 1a ), R₂N(CH₂)₂N(CH₂‐2‐O‐3‐R¹‐5‐R²‐C₆H₂)₂TiCl₂ (R = Me, R¹, R² = tBu ( 2a ), R = iPr, R¹, R² = tBu ( 2b ), R = iPr, R¹ = tBu, R² = OMe ( 2c )), and Me₂N(CH₂)₂N(CH₂‐2‐O‐3,5‐tBu₂‐C₆H₂)(CH₂‐2‐O‐C₆H₄)TiCl₂ ( 2d ) are used in ethylene and propylene homopolymerization, and ethylene/1‐octene copolymerization. All complexes, upon their activation with Al(iBu)₃/Ph₃CB(C₆F₅)₄, exhibit reasonable catalytic activity for ethylene homo‐ and copolymerization giving linear polyethylene with high to ultra‐high molecular weight (600·× 10³–3600·× 10³ g/mol). The activity of 1a /Al(iBu)₃/Ph₃CB(C₆F₅)₄ shows a positive comonomer effect, leading to over 400% increase of the polymer yield, while the addition of 1‐octene causes a slight reduction of the activity of the complexes 2a‐2d . The complexes with the NMe₂ donor group ( 2a , 2d , 1a ) display a high ability to incorporate a comonomer (up to 9–22 mol%), and the use of a bulkier donor group, N(iPr)₂ ( 2b , 2c ), results in a lower 1‐octene incorporation. All the produced copolymers reveal a broad chemical composition distribution. In addition, the investigated complexes polymerized propylene with the moderate ( 1a , 2a ) to low ( 2b‐2d ) activity, giving polymers with different microstructures, from purely atactic to isotactically enriched (mmmm = 28%). © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 2467–2476     

Synthesis,Crystal Structure,and Magnetic Properties of {[Cu(phen)]2(C4H2O4)2} · 4.5H2O with C4H4O4 = Maleic Acid

Reaction of CuCl₂ · 2H₂O, phenanthroline, maleic acid and NaOH in CH₃OH/H₂O (1:1 v/v) at pH = 7.0 yielded blue {[Cu(phen)]₂(C₄H₂O₄)₂} · 4.5H₂O, which crystallizes in the monoclinic space group C2/c (no. 15) with cell dimensions: a = 18.127(2)Å, b = 12.482(2)Å, c = 14.602(2)Å, β = 103.43(1)°, U = 3213.5(8)ų, Z = 4. The crystal structure consists of the centrosymmetric dinuclear {[Cu(phen)]₂(C₄H₂O₄)₂} complex molecules and hydrogen bonded H₂O molecules. The Cu atoms are each square‐pyramidally coordinated by two N atoms of one phen ligand and three carboxyl O atoms of two maleato ligands with one carboxyl O atom at the apical position (d(Cu‐N) = 2.008, 2.012Å, equatorial d(Cu‐O) = 1.933, 1.969Å, axial d(Cu‐O) = 2.306Å). Two square‐pyramids are condensed via two apical carboxyl O atoms with a relatively larger Cu···Cu separation of 3.346(1)Å. The dinuclear complex molecules are assembled via the intermolecular π—π stacking interactions into 1D ribbons. Crossover of the resulting ribbons via interribbon π—π stacking interactions forms a 3D network with the tunnels occupied by H₂O molecules. The title complex behaves paramagnetically between 5—300 K, following the Curie‐Weiss law _χm(T—θ) = 0.435 cm³ · mol^—1 · K with θ = 1.59 K.     

Synthesis and Characterization of Metal Complexes (M = Al,Ti, W,Zn) Containing Pyrrole‐imine Ligands

A series of metal compounds (M = Al, Ti, W, and Zn) containing pyrrole‐imine ligands have been prepared and structurally characterized. The reactions of AlMe₃ with one and three equivs of pyrrole‐imine ligand [C₄H₃NH‐(2‐CH=N? CH₂Ph)] ( 1 ) generated aluminum compounds Al[C₄H₃N‐(2‐CH=N? CH₂Ph)]Me₂ ( 2 ) and Al[C₄H₃N‐(2‐CH=NCH₂Ph)]₃ ( 3 ), respectively, in relatively high yield. Reacting two equivs of 1 with Ti(OⁱPr)₄, W(NH^tBu)₂(=N^tBu)₂, or ZnMe₂ afforded Ti[C₄H₃N‐(2‐CH=NCH₂Ph)]₂(OⁱPr)₂ ( 4 ), W[C₄H₃N‐(2‐CH=NCH₂Ph)]₂(=N^tBu)₂ ( 5 ), and Zn[C₄H₃N‐(2‐CH=NCH₂Ph)]₂ ( 6 ), respectively. All the compounds have been characterized by ¹H and ¹³C NMR spectroscopy. Compounds 3 – 6 have also been characterized by single‐crystal X‐ray structural analysis. The biting angles of pyrrole‐imine ligand with metals decrease and their related M? N_pyrrole and M? N_imine bond lengths increase in the order of 6 , 3 , 4 , and 5 .     

Synthesis and Structures of New Oxidation/ Cycloaddition Products of λ3‐Cyclodiphosphazanes

Reaction of the cyclodiphosphazane [(OC₄H₈N)P(μ‐N‐t‐Bu)₂P(HN‐t‐Bu)] ( 1 ) with an equimolar quantity of diisopropyl azodicarboxylate afforded the phosphinimine product [(OC₄H₈N)P(μ‐N‐t‐Bu)₂P=N‐t‐Bu)(N(CO₂ ‐i‐Pr)NHCO₂‐i‐Pr] ( 6 ) having a P^III‐N‐P^V skeleton. Similar products [(t‐BuNH)P(μ‐N‐t‐Bu)₂P=N‐t‐Bu)(N(CO₂Et)NHCO₂Et] ( 7 ) and [(CO₂‐i‐Pr)HNN(CO₂‐i‐Pr)](t‐BuN=P(μ‐N‐t‐Bu)₂POCH₂CMe₂CH₂O[P(μ‐N‐t‐Bu)₂P=N‐t‐Bu)(N(CO₂‐i‐Pr)NH(CO₂‐i‐Pr)] ( 8 ) were spectroscopically characterized in the reaction of [(t‐BuNH)P‐N‐t‐Bu]₂ ( 2 ) and [(t‐BuNH)P(μ‐N‐t‐Bu)₂POCH₂CMe₂CH₂OP(μ‐N‐t‐Bu)₂P(NH‐t‐Bu)] ( 3 ) with diethyl‐ and diisopropyl azodicarboxylate, respectively. By contrast, the reaction of [(μ‐t‐BuN)P]₂[O‐6‐t‐Bu‐4‐Me‐C₆H₂]₂CH₂ ( 4 ) and [(C₅H₁₀N)P‐μ‐N‐t‐Bu]₂ ( 5 ) with diisopropyl azodicarboxylate afforded the mono‐ and bis‐oxidized compounds [(O)P(μ‐N‐t‐Bu)₂P][O‐6‐t‐Bu‐4‐Me‐C₆H₂]₂CH₂ ( 9 ) and [(C₅H₁₀N)(O)P‐μ‐N‐t‐Bu]₂ ( 10 ), respectively. Oxidative addition of o‐chloranil to 7 and its DIAD analogue [(t‐BuNH)P(μ‐N‐t‐Bu)₂P=N‐t‐Bu)(N(CO₂‐i‐Pr)NHCO₂‐i‐Pr] ( 11 ) afforded [(C₆Cl₄‐1, 2‐O₂)(t‐BuNH)P(μ‐N‐t‐Bu)₂P=N‐t‐Bu)(N(CO₂R)NHCO₂R] [R = Et ( 12 ) and i‐Pr ( 13 )] containing tetra‐ and pentacoordinate P^V atoms in the cyclodiphosphazane ring. The structures of 6 , 9 , 12 and 13 have been confirmed by X‐ray structure determination. For comparison, the X‐ray structure of the double cycloaddition product [(C₆Cl₄‐1, 2‐O₂)(t‐BuNH)PN‐t‐Bu]₂ ( 14 ), obtained from the reaction of 2 with two mole equivalents of o‐chloranil is also reported.     

An oxo‐bridged centrosymmetric tetranuclear titanium compound

The title compound, octa‐tert‐butoxybis­[μ₃‐2,2′‐(N‐methyl­imino)­diethanolato]­di‐μ‐oxo‐tetratitanium(IV), [Ti₂O{(OCH₂CH₂)₂(NCH₃)}{(CH₃)₃CO}₄]₂ or [Ti₄(C₅H₁₁NO₂)₂(C₄H₉O)₈O₂], lies about an inversion centre, and displays the less usual zigzag configuration. One O atom of the N‐methyl­diethoxo­amine ligand bridges the symmetry‐related Ti atoms, while the other bridges the two independent Ti atoms, with the N atom binding to give a facial configuration. Four ^tBuO⁻ ligands and a bridging oxide complete the respective five‐ and sixfold coordination of the two Ti atoms. The Ti—O bond lengths range in a self‐consistent fashion from 1.7624 (17) to 2.0878 (18) Å, while the Ti—N bond length is 2.374 (2) Å.     

The Iminoborane tBuB≡NtBu as a Dipolarphile in (2+3) Cycloadditions

The iminoborane tBuB≡NtBu and the diazomethane tBuCH=N₂ give the (2+3) cycloadduct [—HC(tBu)—N=N—N(tBu)=B(tBu)—] in a 1:1 reaction and the seven‐membered ring [—C(tBu)=N—NH—N(tBu)=B(tBu)—N(tBu)=B(tBu)—] in a 2:1 reaction. The (2+3) cycloadduct decomposes above 0 °C to give the seven‐membered ring, N₂, and HC(tBu)=N—N=CH(tBu) in the ratio 2:1:1. The borane tBuB≡NtBu and organic azides R″N₃ yield the (2+3) cycloadducts [—R″N—N=N—N(tBu)=B(tBu)—] (R″ = Me, Et, Pr, Bu, iBu, sBu, C₅H₁₁, c‐C₅H₉, c‐C₆H₁₁, Bzl, EtOOC).     

1‐Azonia‐2‐boratanaphthalenes

The 1‐azonia‐2‐boratanaphthalenes (NH)(BX)C₈H₆ can be synthesized from 2‐aminostyrene and the dihaloboranes XBHal₂ ( 1 ‐ 4 : X = Cl, Br, iPr, tBu). Further derivatives (NH)(BX)C₈H₆ are obtained from 1 by replacing Cl by alkoxy or alkyl groups [ 5 ‐ 8 : X = OMe, OtBu, Me, (CH₂)₃NMe₂]. The hydrolysis of 1 gives a mixture of the bis(azoniaboratanaphthyl) oxide [(NH)BC₈H₆]₂O ( 9 ) and the hydroxy derivative (NH)[B(OH)]C₈H₆ ( 10 ). The diboryl oxide 9 crystallizes in the space group C2/c. The lithiation of 4 at the nitrogen atom gives [NLi(tmen)](BtBu)C₈H₆ ( 11 ), which upon reaction with the diborane(4) B₂Cl₂(NMe₂)₂ yields the 1, 2‐bis(azoniaboratanaphthyl)diborane B₂[N(BtBu)C₈H₆]₂(NMe₂)₂ ( 12 ). The 2‐chloro‐1‐methyl‐4‐phenyl derivative (NMe)(BCl)C₈H₅Ph ( 13 ) of the parent (NH)(BH)C₈H₆ can be synthesized from the aminoborane BCl₂(NMePh) and phenylethyne. Substitution of Cl in 13 gives the derivatives (NMe)(BX)C₈H₅Ph [ 14 ‐ 20 : X = N(SiMe₃)₂, Me, Et, iBu, tBu, CH₂SiMe₃, Ph] and the reaction of 13 with Li₂O affords the bis(azoniaboratanaphthyl) oxide [(NMe)BC₈H₅Ph]₂O ( 21 ). The reaction of 16 or 19 with [(MeCN)₃Cr(CO)₃] yields the complexes [{(NMe)(BX)C₈H₅Ph}Cr(CO)₃] ( 22 , 23 : X = Et, CH₂SiMe₃), in which the chromium atom is hexahapto bound to the homoarene part of 16 or 19 , respectively. The complex 23 crystallizes in the space group P2₁/c. Upon reaction of the phenols para‐C₆H₄R(OH) with the aryldichloroboranes ArBCl₂ and subsequent condensation of the products with phenylethyne, the 1‐oxonia‐2‐boratanaphthalenes O(BAr)C₈H₄RPh with R in position 6 and Ph in position 4 are formed ( 24 ‐ 26 : Ar = Ph, R = H, Me, OMe; 27 ‐ 29 : Ar = C₆F₅, R = H, Me, OMe). The azoniaboratanaphthalenes 1 ‐ 23 were characterized by NMR methods.     

A new route for the synthesis of phosphate esters: 2,2′‐[benzene‐1,2‐diylbis(oxy)]bis(5,5‐dimethyl‐1,3,2‐dioxaphosphinane) 2,2′‐dioxide

Podand‐type ligands are an interesting class of acyclic ligands which can form host–guest complexes with many transition metals and can undergo conformational changes. Organic phosphates are components of many biological molecules. A new route for the synthesis of phosphate esters with a retained six‐membered ring has been used to prepare 2,2′‐[benzene‐1,2‐diylbis(oxy)]bis(5,5‐dimethyl‐1,3,2‐dioxaphosphinane) 2,2′‐dioxide, C₆H₄{O[cyclo‐P(O)OCH₂CMe₂CH₂O]}₂ or C₁₆H₂₄O₈P₂, (1), 2‐[(2′‐hydroxybiphenyl‐2‐yl)oxy]‐5,5‐dimethyl‐1,3,2‐dioxaphosphinane 2‐oxide, [cyclo‐P(O)OCH₂CMe₂CH₂O](2,2′‐OC₆H₄–C₆H₄OH), (2), and oxybis(5,5‐dimethyl‐1,3,2‐dioxaphosphinane) 2,2′‐dioxide, O[cyclo‐P(O)OCH₂CMe₂CH₂O]₂, (3). Compound (1) is novel, whereas the results for compounds (2) and (3) have been reported previously, but we record here our results for compound (3), which we find are more precise and accurate than those currently reported in the literature. In (1), two cyclo‐P(O)OCH₂CMe₂CH₂O groups are linked through a catechol group. The conformations about the two catechol O atoms are quite different, viz. one C—C—O—P torsion angle is −169.11 (11)° and indicates a trans arrangement, whereas the other C—C—O—P torsion angle is 92.48 (16)°, showing a gauche conformation. Both six‐membered POCCCO rings have good chair‐shape conformations. In both the trans and gauche conformations, the catechol O atoms are in the axial sites and the short P=O bonds are equatorially bound.     

Preparation and Characterization of Aluminum Alkoxides and their Application to Ring‐Opening Polymerization of ϵ‐Caprolactones

The reaction of 2‐methoxybenzyl alcohol with one molar equiv of R₂AIX in diethyl ether at 0°C gives [(2‐MeOC₆H₄CH₂‐μ‐O)AlRX]₂ ( 1 : R = Et, X = Cl, 2 : R = X = Et). In addition, 2,4‐di‐tert‐butylphenol reacts with ⁱBu₃Al affording a four‐coordinated aluminum compound [(μ‐2,4‐^tBu₂‐C₆H₄O)Al(ⁱBu)₂]₂ ( 4 ). Single crystal X‐ray structure analysis of 4 shows a C_2h‐symmetry with a planar Al₂O₂ core. Ring‐opening polymerization (ROP) of caprolactones initiated by 1, 4 and [(μ‐OCH₂C₆H₄OMe)Al(ⁱBu)₂]₂ ( 3 ) is performed and polyesters with narrow molecular weight distributions were obtained from the “living” ROP of caprolactones. ¹H NMR spectroscopic studies of PCL reveal that the initiator of 1 and 3 is through the Al‐OAr function, but the initiator of 4 is through the Al‐ ⁱBu group.     

Crystal Structure of a Trinuclear Titanium(IV) Complex with (rac)‐3,3′‐Bis(methoxymethyl)‐BINOLate

Reaction of (rac)‐3,3′‐bis(methoxymethyl)‐BINOL [H₂(CH₃OCH₂)₂BINO] with excess Ti(OⁱPr)₄ and one equivalent of H₂O in CH₂Cl₂ affords a trinuclear titanium(IV) complex [{(CH₃OCH₂)₂BINO}Ti₃(μ₃‐O)(OiPr)₆(μ₂‐OiPr)₂]. By dissolving it in dichloromethane and hexane and cooling to 0 °C, plate‐like pale yellow single crystals (monoclinic, P2₁/n, a = 12.605(3), b = 21.994(5), c = 19.090(4) Å, β = 92.764(8)°, V = 5286.2(19) ų, T = 293(2) K) were obtained. Each oxygen atom at 2 or 2′ position of the (CH₃OCH₂)₂BINO ligand bonds to only one titanium atom. There is no interaction between the third Ti atom and the two oxygen atoms of 3,3′‐bis(methoxymethyl)‐BINOLate.     

The dimeric mixed‐ligand titana­carborane sandwich [1‐(Cp)‐1‐Ti‐2‐(Me)‐3‐(SiMe3)‐2,3‐C2B4H4]2

The title dimer, bis­[1‐cyclo­penta­dienyl‐2‐methyl‐1‐titana‐3‐tri­methylsilyl‐2,3‐dicarba‐closo‐hexaborane(6)], [Ti(C₅H₅)(C₆­H₁₆­B₄Si)]₂, reveals that the centrosymmetric mol­ecule consists of two bent‐sandwich titanacarboranes bridged by the B—H—Ti bonds. The average bond distances are Ti—B 2.445 (3), Ti—C(cage) 2.334 (2) and Ti—C(Cp) 2.376 (3) Å, and the corresponding bond angles are Cp—Ti—Cp 163.2 (1) and Cp—Ti—Cb (Cb = C₂B₃ face) 139.9 (1)°; the Ti—H separations are 2.10 (2) and 2.19 (2) Å.     

A Sterically Hindered Phosphonic Acid with a Hydrogen‐Bonded Cage Structure: [4‐tert‐Bu‐2,6‐Mes2‐C6H2P(O)(OH)2·H2O]4

The synthesis and molecular structure of the novel phosphonic acid 4‐tert‐Bu‐2,6‐Mes₂‐C₆H₂P(O)(OH)₂ ( 1 ) is reported. Compound 1 crystallizes in form of its monohydrate as a hydrogen‐bonded cluster ( 1·H₂O )₄ comprizing four phosphonic acid molecules (O···O 2.383(3)‐3.006(4) Å). Additionally, sterically hindered terphenyl‐substituted phosphorus compounds of the type 4‐tert‐Bu‐2,6‐Mes₂‐C₆H₂PR(O)(OH) ( 5 , R = H; 7 , R = O₂CC₆H₄‐3‐Cl; 9 , R = OEt) were prepared, which all show dimeric hydrogen‐bonded structures with O···O distances in the range 2.489(2)–2.519(3) Å. Attempts at oxidizing 5 using H₂O₂, KMnO₄, O₃, or Me₃NO in order to give 1 failed. Crystallization of 5 in the presence of Me₃NO gave the novel hydrogen bonded aggregate 4‐tert‐Bu‐2,6‐Mes₂‐C₆H₂PH(O)(OH)·ONMe₃ ( 6 ) showing an O–H···O distance of 2.560(4) Å.     

Isomorphous rare‐earth bis[bis(2,6‐diisopropylphenyl)phosphate] complexes and their self‐assembly into two‐dimensional frameworks by intramolecular hydrogen bonds

The crystal structures of rare‐earth diaryl‐ or dialkylphosphate derivatives are poorly explored. Crystals of bis[bis(2,6‐diisopropylphenyl)phosphato‐κO ]chloridotetrakis(methanol‐κO )neodymium methanol disolvate, [Nd(C₂₄H₃₄O₄P)Cl(CH₄O)₄]·2CH₃OH, (1), and of the lutetium, [Lu(C₂₄H₃₄O₄P)Cl(CH₄O)₄]·2CH₃OH, (2), and yttrium, [Y(C₂₄H₃₄O₄P)Cl(CH₄O)₄]·2CH₃OH, (3), analogues have been obtained by reactions between lithium bis(2,6‐diisopropylphenyl)phosphate and LnCl₃(H₂O)₆ (in a 2:1 ratio) in methanol. Compounds (1)–(3) crystallize in the C 2/c space group. Their crystal structures are isomorphous. The molecule possesses C ₂ symmetry with a twofold crystallographic axis passing through the Ln and Cl atoms. The bis(2,6‐diisopropylphenyl)phosphate ligands all display a κ¹O‐monodentate coordination mode. The coordination polyhedron for the metal atom [coordination number (CN) = 7] is a distorted pentagonal bipyramid. Each [Ln{O₂P(O‐2,6‐ⁱPr₂C₆H₃)₂}₂Cl(CH₃OH)₄] molecular unit exhibits two intramolecular O—H…O hydrogen bonds, forming six‐membered rings, and two intramolecular O—H…Cl interactions, forming four‐membered rings. Intermolecular O—H…O hydrogen bonds connect each unit via four noncoordinating methanol molecules with four other units, forming a two‐dimensional hydrogen‐bond network. Crystals of bis[bis(2,6‐diisopropylphenyl)phosphato‐κO ]tetrakis(methanol‐κO )(nitrato‐κ²O ,O ′)neodymium methanol disolvate, [Nd(C₂₄H₃₄O₄P)(NO₃)(CH₄O)₄]·2CH₃OH, (4), have been obtained in an analogous manner from NdCl₃(H₂O)₆. Compound (4) also crystalizes in the C 2/c space group. Its crystal structure is similar to those of (1)–(3). The κ²O ,O ′‐bidentate nitrate anion is disordered over a twofold axis, being located nearly on it. Half of the molecule is crystallographically unique (CN_Nd = 8). Unlike (1)–(3), complex (4) exhibits disorder of all three methanol molecules, one isopropyl group of the phosphate ligand and the NO₃⁻ ligand. The structure of (4) displays intra‐ and intermolecular O—H…O hydrogen bonds similar to those in (1)–(3). Compounds (1)–(4) represent the first reported mononuclear bis[bis(diaryl/dialkyl)phosphate] rare‐earth complexes.     

Ruthenium(II) Complexes Bearing Schiff Base Ligands for Efficient Acceptorless Dehydrogenation of Secondary Alcohols†

Four ruthenium(II) complexes 1—4 [RN=CH‐(2,4‐(^tBu)₂C₆H₂O)]RuH(PPh₃)₂(CO) (R = C₆H₅, 1; R = 4‐MeC₆H₄, 2; R = 4‐ClC₆H₄, 3; R = 4‐BrC₆H₄, 4) bearing Schiff base ligands were prepared by treating RuHClCO(PPh₃)₃ with RN=CH‐(2,4‐(^tBu)₂C₆H₂OH (L1—L4) in the presence of triethylamine. Their structures were fully characterized by elemental analysis, IR, NMR spectroscopy and X‐ray crystallography. These Ru(II) complexes exhibit high catalytic performance and good functional‐group compatibility in the acceptorless dehydrogenation of secondary alcohols, affording the corresponding ketones in 82%—94% yields.     

catena‐Poly­[[di­aqua­cadmium(II)]‐μ‐5‐carboxyimidazole‐4‐carboxylato‐κ4N1,O5:O4,N3]

A new cadmium coordination polymer, [Cd(C₅H₂N₂O₄)(H₂O)₂]_n, possesses a one‐dimensional zigzag chain structure built from Cd^II centers bridged sequentially by pairs of O and N atoms of the 5‐carboxyimidazole‐4‐carboxylate ligand. The Cd^II center is in a distorted octahedral geometry, being coordinated by two O atoms from two coordinated water mol­ecules [Cd—O = 2.322 (7) and 2.364 (7) Å], and by two N atoms [Cd—N = 2.222 (6) and 2.232 (6) Å] and two carboxyl O atoms [Cd—O = 2.383 (6) and 2.414 (6) Å] from two 5‐carboxyimidazole‐4‐carboxylate ligands.     

Synthese und Struktur der Nitrido‐Komplexe [(n‐Bu)4N]2[{(L)Cl4Re≡N}2PtCl2] (L = THF und H2O) und [(n‐Bu)4N]2[(H2O)Cl4Re≡N‐PtCl(μ‐Cl)]2

Synthesis and Crystal Structure of the Nitrido Complexes [(n‐Bu)₄N]₂[{(L)Cl₄Re≡N}₂PtCl₂] (L = THF und H₂O) and [(n‐Bu)₄N]₂[(H₂O)Cl₄Re≡N‐PtCl(μ‐Cl)]₂ The threenuclear complex [(n‐Bu)₄N]₂[{(THF)Cl₄Re≡N}_2—PtCl₂] ( 1a ) is obtained by the reaction of [(n‐Bu)₄N][ReNCl₄] with [PtCl₂(C₆H₅CN)₂] in THF/CH₂Cl₂. It forms red crystals with the composition 1a · 2 CH₂Cl₂ crystallizing in the tetragonal space group I4₁/a with a = 3186.7(2); c = 1311.2(1) pm and Z = 8. If the reaction of the educts is carried out without THF, however under exposure to air the compound [(n‐Bu)₄N]₂[{(H₂O)Cl₄Re≡N}₂PtCl₂] ( 1b ) is obtained as red trigonal crystals with the space group R3 and a = 3628.3(3), c = 1231.4(1) pm and Z = 9. In the centrosymmetric complex anions [{(L)Cl₄Re≡N}₂PtCl₂]^2— a linear PtCl₂moiety is connected in a trans arrangement with two complex fragments [(L)Cl₄Re≡N]^— via asymmetric nitrido bridges Re≡dqN‐Pt. For Pt^II such results a square‐planar coordination PtCl₂N₂. The linear nitrido bridges are characterized by distances Re‐N = 169.5 pm and Pt‐N = 188.8 pm ( 1a ), respectively, Re‐N = 165.6 pm and Pt‐N = 194.1 pm ( 1b ). By the reaction of [(n‐Bu)₄N][ReNCl₄] with PtCl₄ in CH₂Cl₂ platinum is reduced forming the heterometallic Re^VI/Pt^II complex, [(n‐Bu)₄N]₂[(H₂O)Cl₄Re≡N‐PtCl(μ‐Cl)]₂ ( 2 ). It crystallizes in the monoclinic space group C2/c with a = 2012.9(1); b = 1109.0(2); c = 2687.4(4) pm; β = 111.65(1)° and Z = 4. In the central unit ClPt(μ‐Cl)₂PtCl of the anionic complex [(H₂O)Cl₄Re≡N‐PtCl(μ‐Cl)]₂^2— with the symmetry C₂ the coordination of the Pt atoms is completed by two nitrido bridges Re≡N‐Pt to nitrido complex fragments [(H₂O)Cl₄Re≡N] ^— forming a square‐planar arrangement for the Pt atoms. The distances in the linear nitrido bridges are Re‐N = 165.9 pm and Pt‐N = 190.1 pm.     

Crystal Structures of [Mn2(H2O)4(phen)2(C4H4O4)2] · 2 H2O and [Mn(phen)2(H2O)2][Mn(phen)2(C4H4O4)](C4H4O4) · 7 H2O

Reactions of 1,10‐phenanthroline monohydrate, Na₂C₄H₄O₄ · 6 H₂O and MnSO₄ · H₂O in CH₃OH/H₂O yielded a mixture of [Mn₂(H₂O)₄(phen)₂(C₄H₄O₄)₂] · 2 H₂O ( 1 ) and [Mn(phen)₂(H₂O)₂][Mn(phen)₂(C₄H₄O₄)](C₄H₄O₄) · 7 H₂O ( 2 ). The crystal structure of 1 (P1 (no. 2), a = 8.257(1) Å, b = 8.395(1) Å, c = 12.879(2) Å, α = 95.33(1)°, β = 104.56(1)°, γ = 106.76(1)°, V = 814.1(2) ų, Z = 1) consists of the dinuclear [Mn₂(H₂O)₄(phen)₂(C₄H₄O₄)₂] molecules and hydrogen bonded H₂O molecules. The centrosymmetric dinuclear molecules, in which the Mn atoms are octahedrally coordinated by two N atoms of one phen ligand and four O atoms from two H₂O molecules and two bis‐monodentate succinato ligands, are assembled via π‐π stacking interactions into 2 D supramolecular layers parallel to (101) (d(Mn–O) = 2.123–2.265 Å, d(Mn–N) = 2.307 Å). The crystal structure of 2 (P1 (no. 2), a = 14.289(2) Å, b = 15.182(2) Å, c = 15.913(2) Å, α = 67.108(7)°, β = 87.27(1)°, γ = 68.216(8)°, V = 2934.2(7) ų, Z = 2) is composed of the [Mn(phen)₂(H₂O)₂]²⁺ cations, [Mn(phen)₂(C₄H₄O₄)] complex molecules, (C₄H₄O₄)^2– anions, and H₂O molecules. The (C₄H₄O₄)^2– anions and H₂O molecules form 3 D hydrogen bonded network and the cations and complex molecules in the tunnels along [001] and [011], respectively, are assembled via the π‐π stacking interactions into 1 D supramolecular chains. The Mn atoms are octahedrally coordinated by four N atoms of two bidentate chelating phen ligands and two water O atoms or two carboxyl O atoms (d(Mn–O) = 2.088–2.129 Å, d(Mn–N) = 2.277–2.355 Å). Interestingly, the succinato ligands in the complex molecules assume gauche conformation bidentately to chelate the Mn atoms into seven‐membered rings.     

Two Glutarato Bridged Coordination Polymers: ${_{\infty}^1}${[Mn(phen)]2L4/2} and ${_{\infty}^1}${[Zn(phen)(H2O)]L2/2}·H2O with H2L = Glutaric Acid

Two new glutarato bridged coordination polymers {[Mn(phen)]₂(C₅H₆O₄)_4/2} ( 1 ) and {[Zn(phen)(H₂O)](C₅H₆O₄)_2/2}· H₂O ( 2 ) were structurally characterized on the basis of single crystal X‐ray diffraction data. Crystal data: ( 1 ) P2/c (no. 13), a = 10.340(2)Å, b = 10.525(2)Å, c = 13.891(2)Å, β = 98.31(1)°, U = 1495.9(5)ų, Z = 2; ( 2 ) P2₁/n (no. 14), a = 6.738(1)Å, b = 25.636(3)Å, c = 10.374(1)Å, β = 106.13(1)°, U = 1721.4(4)ų, Z = 4. Complex 1 consists of 1D ribbon‐like {[Mn(phen)]₂(C₅H₆O₄)_4/2} chains, in which the [Mn(phen)] units were interlinked by glutarato ligands to generate 8‐ and 16‐membered rings. The Mn atoms are octahedrally coordinated by two N atoms of one phen ligand and four O atoms of three glutarato ligands with d(Mn‐N) = 2.270, 2.276Å, d(Mn‐O) = 2.114—2.283Å. Through the interchain π‐π stacking interactions, the 1D chains are assembled into 2D puckered layers, which are further held together by interlayer π‐π stacking interactions into a 3D network. Complex 2 is built up by 1D {[Zn(phen)(H₂O)](C₅H₆O₄)_2/2} linear chains and hydrogen bonded H₂O molecules. The Zn atoms are coordinated by two N atoms of one phen ligand and three O atoms of one H₂O molecule and two glutarato ligands to form slightly elongated trigonal bipyramids with the water O atom and one phen N atom at the apical positions (d(Zn‐N) = 2.101, 2.168Å, d(Zn‐O) = 1.991—2.170Å). The 1D linear chains result from [Zn(phen)(H₂O)] units bridged by bis‐monodentate glutarato ligands. The resulting 1D chains are assembled by π‐π stacking interactions into 2D layers, between which the hydrogen bonded H₂O molecules are situated.     

Supramolecular Assemblies of Mononuclear and Polymeric Nickel(II) Glutarato Complexes via π‐π Stacking Interactions and Hydrogen Bonds: [Ni(H2O)3(phen)(C5H6O4)] · H2O and [Ni(H2O)2(phen)(C5H6O4)]

Syntheses of the sky blue complex compounds [Ni(H₂O)₃(phen)(C₅H₆O₄)] · H₂O ( 1 ) and [Ni(H₂O)₂(phen)(C₅H₆O₄)] ( 2 ) were carried out by the reactions of 1,10‐phenanthroline monohydrate, glutaric acid, NiSO₄ · 6 H₂O and Na₂CO₃ in CH₃OH/H₂O at pH = 6.9 and 7.5, respectively. The crystal structure of 1 (P 1 (no. 2), a = 14.289 Å, b = 15.182 Å, c = 15.913 Å, α = 67.108°, β = 87.27°, γ = 68.216°, V = 2934.2 ų, Z = 2) consists of hydrogen bonded [Ni(H₂O)₃‐ (phen)(C₅H₆O₄)]₂ dimers and H₂O molecules. The Ni atoms are octahedrally coordinated by two N atoms of one phen ligand, three water O atoms and one carboxyl O atom from one monodentate glutarato ligand (d(Ni–N) = 2.086, 2.090 Å; d(Ni–O) = 2.064–2.079 Å). Through the π‐π stacking interactions and intermolecular hydrogen bonds, the dimers are assembled to form 2 D layers parallel to (0 1 1). The crystal structure of 2 (P2₁/n (no. 14), a = 7.574 Å, b = 11.938 Å, c = 18.817 Å, β = 98.48°, V = 1682.8 ų, Z = 4) contains [Ni(H₂O)₂(phen)(C₅H₆O₄)_2/2] supramolecular chains extending along [010]. The Ni atoms are octahedrally coordinated by two N atoms of one phen ligand, two water O atoms and two carboxyl O atoms from different bis‐monodentate glutarato ligands with d(Ni–N) = 2.082, 2.105 Å and d(Ni–O) = 2.059–2.087 Å. The supramolecular chains are assembled into a 3 D network by π‐π stacking interactions and interchain hydrogen bonds. A TG/DTA of 2 shows two endothermic effects at 132 °C and 390 °C corresponding to the complete dehydration and the lost of phen.     

Crystal Structures of {[Cd(phen)](C6H8O4)3/3} and {[Cd(phen)](C7H10O4)3/3} · 2H2O with C6H10O4 = Adipic Acid and C7H12O4 = Pimelic Acid

Two coordination polymers {[Cd(phen)](C₆H₈O₄)_3/3} ( 1 ) and {[Cd(phen)](C₇H₁₀O₄)_3/3} · 2H₂O ( 2 ) were structurally characterized by single crystal X‐ray diffraction methods. In 1 (C2/c (no. 15), a = 16.169(2)Å, b = 15.485(2)Å, c = 14.044(2)Å, β = 112.701(8)°, U = 3243.9(7)ų, Z = 8), the Cd atoms are coordinated by two N atoms of one phen ligand and five O atoms of three adipato ligands to form mono‐capped trigonal prisms with d(Cd‐O) = 2.271‐2.583Å and d(Cd‐N) = 2.309, 2.390Å. The [Cd(phen)] moieties are bridged by adipato ligands to generate {[Cd(phen)](C₆H₈O₄)_3/3} chains, which, via interchain π—π stacking interactions, are assembled into layers. Complex 2 (P1¯(no. 2), a = 9.986(1)Å, b = 10.230(3)Å, c = 11.243(1)Å, α = 66.06(1)°, β = 87.20(1)°, γ = 66.71(1)°, U = 955.7(2)ų, Z = 2) consists of {[Cd(phen)](C₇H₁₀O₄)_3/3} chains and hydrogen bonded H₂O molecules. The Cd atoms are pentagonal bipyramidally coordinated by two N atoms of one phen ligand and five O atoms of three pimelato ligands with d(Cd‐O) = 2.213—2.721Å and d(Cd‐N) = 2.329, 2.372Å. Through interchain π—π stacking interactions, the {[Cd(phen)](C₇H₁₀O₄)_3/3} chains resulting from [Cd(phen)] moieties bridged by pimelato ligands are assembled in to layers, between which the hydrogen bonded H₂O molecules are sandwiched.