Nitridorhenium(V)‐Komplexe mit Dimercaptobernsteinsäuredimethylester. Präparation,Charakterisierung und Kristallstruktur von [Re{NC(CH3)2PPhMe2}(DMSMe2)2]

Nitridorhenium(V) Complexes with Dimercapto Succinic Acid Dimethylester. Preparation, Characterization, and Crystal Structure of [Re{NC(CH₃)₂PPhMe₂}(DMSMe₂)₂] Reaction of [ReNCl₂(Me₂PhP)₃] 1 with two equivalents of dimercaptosuccinic acid dimethylester (DMSMe₂) results in the formation of a neutral, diamagnetic rhenium(V)‐DMSMe₂ complex with a phenyldimethylphosphinoisopropyl group at the nitrido ligand as a consequence of a nucleophilic attack of the coordinated nitrido ligand on the solvent molecule. The formed complex 2 of the composition [Re{NC(CH₃)₂(Me₂PhP)}(DMSMe₂)₂] crystallizes in the triclinic space group P 1, a = 12.334(7), b = 12.412(7), c = 12.414(8) Å; α = 60.14(3)°, β = 67.98(3)°, γ = 80.63(6)°; Z = 2. Rhenium is located in a square‐pyramidal configuration of the donor atoms. The two meso‐DMSMe₂ ligands are in a syn‐endo conformation. The rhenium‐nitrogen bond (1.697(12) Å) is only slightly longer than typical Re–N bonding distances in nitrido complexes and comparable with other Re–N–C bonding distances. The addition of a solvent molecule is observed in acetone ( 2 ) as well as in methylethylketone ( 3 ). Moreover, a reaction of the nitrido group with the condensation product of ketone is found by mass spectrometry ([ReN{C(CH₃)(C₂H₅)CH₂C(O)C₂H₅(Me₂PhP)}(DMSMe₂)₂] 4 ).     

Synthese und Strukturen von [ReNBr2(Me2PhP)3] und (Me2PhPH)[fac‐Re(NBBr3)Br3(Me2PhP)2]

Syntheses and Structures of [ReNBr₂(Me₂PhP)₃] and (Me₂PhPH)[ fac ‐Re(NBBr₃)Br₃(Me₂PhP)₂] [ReNBr₂(Me₂PhP)₃] ( 1 ) has been prepared by the reaction of [ReNCl₂(Me₂PhP)₃] with Me₃SiBr in dichloromethane. The bromo complex reacts with BBr₃ under formation of [Re(NBBr₃)Br₂(Me₂PhP)₃] ( 2 ) or (Me₂PhPH)[fac‐Re(NBBr₃)Br₃(Me₂PhP)₂] ( 3 ) depending on the experimental conditions. The formation of the nitrido bridge leads to a significant decrease of the structural trans influence of the nitrido ligand which is evident by the shortening of the Re‐(trans)Br bond from 2.795(1) Å in [ReNBr₂(Me₂PhP)₃] to 2.620(1) Å in [fac‐Re(NBBr₃)Br₃(Me₂PhP)₂]^– and 2.598(1) Å in [Re(NBBr₃)Br₂(Me₂PhP)₃], respectively.     

Gemischtligand-Komplexe des Rheniums. VI. Darstellung und Strukturen der Rhenium?Thionitrosyl-Komplexe mer-[Re(NS)Cl2(Me2PhP)3] · CH2Cl2 und trans-[Re(NS)Cl3(Me2PhP)2]

Mixed-ligand Complexes of Rhenium. VI. Synthesis and X-Ray Structures of the Rhenium Thionitrosyl Complexes mer-[Re(NS)Cl₂(Me₂PhP)₃] · CH₂Cl₂ and trans-[Re(NS)Cl₃(Me₂PhP)₂] mer-Dichlorotris(dimethylphenylphosphine)(thionitrosyl)rhenium(I), mer-[Re(NS)Cl₂(Me₂PhP)₃], and trans-Trichlorobis(dimethylphenylphosphine)(thionitrosyl)rhenium(II), trans-[Re(NS)Cl₃(Me₂PhP)₂], are formed during the reaction of rhenium(V) mixed-ligand complexes of the general formula [ReN(Cl)(Me₂PhP)₂(R₂tcb)] with disulphur dichloride (HR₂tcb = N-(N,N-dialkylthiocarbamoyl)benzamidine). The chelating ligands are substituted during the reaction. mer-[Re(NS)Cl₂(Me₂PhP)₃] crystallizes monoclinic in the space group P2₁/n. The dimensions of the unit cell are a = 8.854(2); b = 31.295(3); c = 11.981(3) Å; β = 108.14(1)°; Z = 4. A final R value of 0.033 was achieved on the basis of 5 387 reflections with I ≥ 3σ(I). The rhenium atom is coordinated in a distorted octahedral environment. The Me₂PhP ligands are arranged meridionally cis to the linear thionitrosyl group. trans-[Re(NS)Cl₃(Me₂PhP)₂] crystallizes in the monoclinic space group C2/c with an unit cell of the dimensions a = 33.320(9); b = 8.446(1); c = 17.28(5) Å; β = 116.09(1)°, Z = 8. The R value converged at 0.026 on the basis of 5 460 independent reflections. The metal is octahedrally coordinated with the phosphine ligands in trans position to each other. The angle Re? N? S is 175.7(3)°.     

Gemischtligand-Komplexe des Rheniums. IV. Die Reaktion von [ReNCl2(Me2PhP)3] mit Dithiocarbamaten. Kristallstrukturen von trans-Chloro-dimethyldithiocarbamato-bis(dimethylphenylphosphan) nitridorhenium(V), [ReN(Cl)(Me2PhP)2(Me2dtc)], und Bis(diethyldithiocarbamato)(dimethylphenylphosphan)nitridorhenium(V), [ReN(Me2PhP)(Et2dtc)2]

Mixed-Ligand Complexes of Rhenium IV. The Reaction of [ReNCl₂(Me₂PhP)₃] with Dithiocarbamates. X-Ray Crystal Structures of trans-Chloro-dimethyldithiocarbamato-bis(dimethylphenylphosphine) nitridorhenium(V), [ReN(Cl)(Me₂PhP)₂(Me₂dtc)], and Bis(diethyldithiocarbamato)(dimethylphenylphosphine)nitridorhenium(V), [ReN(Cl)(Me₂PhP)(Et₂dtc)₂] [ReNCl₂(Me₂PhP)₃] reacts with dialkyldithiocarbamates, R₂dtc^?, under a stepwise ligand exchange. Final products of these reactions are the well-known [ReN(R₂dtc)₂] bischelates. Intermediatelly, however, complexes of the general formulae [ReN(Cl)(Me₂PhP)₂(R₂dtc)] and [ReN(Me₂PhP)(R₂dtc)₂] can be isolated. Representatives have been structurally characterized. [ReN(Cl)(Me₂PhP)₂(Me₂dtc)] crystallizes monoclinic in the space group P2₁/c, Z = 4. The dimensions of the unit cell are a = 13.071(3); b = 11.622(1); c = 15.667(3) Å; β = 97.09(1)°. The rhenium atom has a distorted octahedral environment; the Re≡N bond length is 1.71(1) Å. The Re? Cl bond distance is markedly lengthened (2.665(2) Å) as a consequence of the strong trans labilizing influence of the coordinated nitrido ligand. [ReN(Me₂PhP)(Et₂dtc)₂] crystallizes monoclinic in the space group P2₁/c, Z = 4, a = 17.262(3); b = 14.915(2); c = 9.888(2); β = 76.35(8)°. The equatorial coordination sphere is occupied by one phosphorus atom and three sulphur atoms. One of the dithiocarbamate ligands is coordinated bidentately; the second one with two distinct Re? S bond lengths. The Re? S(4) distance is 2.7983(2) Å which can be discussed as a weak interaction with the metal.     

Gemischtligandkomplexe des Rheniums. IX. Reaktionen am Nitridoliganden von [ReN(Me2PhP)(Et2dtc)2]. Synthese,Charakterisierung und Kristallstrukturen von [Re(NBCl3)(Me2PhP)(Et2dtc)2], [Re(NGaCl3)(Me2PhP)(Et2dtc)2] und [Re(NS)Cl(Me2PhP)2(Et2dtc)]

Mixed-ligand Complexes of Rhenium. IX. Reactions on the Nitrido Ligand of [ReN(Me₂PhP)(Et₂dtc)₂]. Synthesis, Characterization, and Structures of [Re(NBCl₃)(Me₂PhP)(Et₂dtc)₂], [Re(NGaCl₃)(Me₂PhP)(Et₂dtc)₂], and [Re(NS)Cl(Me₂PhP)₂(Et₂dtc)] BCl₃, GaCl₃ and S₂Cl₂ react with the well-known [ReN(Me₂PhP)(Et₂dtc)₂] by attack of the nucleophilic nitrido ligand. Final products of these reactions are [Re(NBCl₃)-(Me₂PhP)(Et₂dtc)₂], [Re(NGaCl₃)(Me₂PhP)(Et₂dtc)₂], and [Re(NS)Cl(Me₂PhP)₂Et₂dtc)] which have been studied by mass spectrometry, IR spectroscopy and X-ray diffraction. [Re(NBCl₃)(Me₂PhP)(Et₂dtc)₂] crystallizes in the triclinic space group P1 , Z = 2, a = 8.151(6), b = 9.935(8), c = 18.67(1) Å; α = 94.42(4), β = 97.09(1), γ = 101.35(4)°. The coordination geometry is a distorted octahedron. The equatorial coordination sphere is occupied by one phosphorus and three sulphur atoms. The fourth sulphur atom is in trans position to the Re?N? B moiety. The almost linear Re?N? B unit has an Re?N? B angle of 170.5(3)° with a Re? N bond length of 1.704(3) Å. The analogous [Re(NGaCl₃)(Me₂PhP)(Et₂dtc)₂] crystallizes in P2₁/c with a = 8.138(3), b = 18.279(2), c = 19.880(6) Å; β = 99.81(2)°; Z = 4. Rhenium has a distorted octahedral environment. The Re? N? Ga bond is slightly bent with an angle of 154.5(4)° and a Re? N bond length of 1.695(6) Å. [Re(NS)Cl(Me₂PhP)₂(Et₂dtc)] crystallizes in the triclinic space group P1 , Z = 4, a = 9.514(2); b = 16.266(5); c = 18.388(3) Å; α = 88.75(2), β = 76.59(2), γ = 85.50(2)° with two crystallographically independent molecules in the asymmetric unit. Rhenium has a distorted octahedral environment with the chloro ligand in trans position to the almost linear thionitrosyl group. The Re?N bond lengths are 1.795(6) and 1.72(1) Å, respectively, and the N?S distances are 1.55(1) and 1.59(1) Å, respectively.     

Darstellung,Strukturen und EPR-Spektren der Rhenium(II)Thionitrosylkomplexe trans-[Re(NS)Cl3(MePh2P)2] und trans-[Re(NS)Br3(Me2PhP)2]

Preparation, Structures, and EPR Spectra of the Rhenium(II) Thionitrosyl Complexes trans -[Re(NS)Cl₃(MePh₂P)₂] and trans -[Re(NS)Br₃(Me₂PhP)₂] The paramagnetic rhenium(II) thionitrosyl compounds trans-[Re(NS)Cl₃(MePh₂P)₂] and trans-[Re(NS)Br₃(Me₂PhP)₂] are characterized by crystal structure diffraction and EPR spectroscopy. Trans-[Re(NS)Cl₃(MePh₂P)₂] is formed during the reduction of (a) [ReNCl₂(MePh₂P)₃] with disulphur dichloride or (b) of mer-[ReCl₃(MePh₂P)₃] with trithiazyl chloride. Trans-[Re(NS)Br₃(Me₂PhP)₂] is the final product of the ligand exchange reaction of mer-[Re(NS)Cl₂(Me₂PhP)₃] with bromine whereby the metal occurred to be simultaneusly oxidized. The crystal structure analyses show for trans-[Re(NS)Cl₃(MePh₂P)₂] (monoclinic, C2/c, a = 13.831(3) Å, b = 13.970(1) Å, c = 14.682(2) Å, β = 95.33(1), Z = 4) and trans-[Re(NS)Br₃(Me₂PhP)₂] (monoclinic, C2/c, a = 33.292(5) Å, b = 8.697(1) Å, c = 17.495(3) Å, β = 115.65(1), Z = 8) linear co-ordinated NS ligands (Re–N–S-angles 180° and 174.8°). The metal atom is octahedrally co-ordinated with the phosphine ligands in trans position to each other. X-band and Q-band EPR spectra of the rhenium(II) thionitrosyl complexes (5 d⁵ “low-spin” configuration, S = 1/2) are detected in the temperature range 295 ≥ T ≥ 130 K. They are characterized by well resolved ^185,187Re hyperfine patterns. The hyperfine parameters are used to get information about the spin-density distribution of the unpaired electron in the complexes under study.     

trans‐[Re(NH3)I2(Me2PhP)3]I3 – Bildung eines Amminaus einem Nitridoliganden

trans ‐[Re(NH₃)I₂(Me₂PhP)₃]I₃ – Formation of an Ammine Ligand from a Nitrido Ligand The reaction of [ReNCl₂(Me₂PhP)₃] (Me₂PhP = dimethylphenylphosphine) with Me₃SiI in dichloromethane results in the formation of trans‐[Re(NH₃)I₂(Me₂PhP)₃]I₃. The unusual protonation of a nitrido ligand is due to the partial decomposition of the solvent.     

Gemischtligandkomplexe des Technetiums. XVI. Darstellung und Struktur von (1,2-Dicyanoethen-1,2-dithiolato)bis(dimethylphenylphosphan)nitridotechnetium (V), [TcN(Me2PhP)2(mnt)]

Mixed-Ligand Complexes of Technetiums. XVI Synthesis and Structure of (1,2-Dicyanoethene-1,2-dithiolato)bis(dimethylphenylphosphine)nitridotechnetium(V), [TcN(Me₂PhP)₂(mnt)] [TcN(Me₂PhP)₂(mnt)] is formed from [TcNCl₂(Me₂PhP)₃] and one equivalent of the sodium salt of 1,2-dicyanoethene-1,2-dithiolate (Na₂mnt). The same reaction yields [TcN(mnt)₂]^2?, when a large excess of the ligand and long reaction periods are applied. The complex anion can be isolated as tetraalkylammonium or tetraphenylarsonium salts. [TcN(Me₂PhP)₂(mnt)] crystallizes in the triclinic space group P1 (a = 10.000(5), b = 14.182(6), c = 17.77(1) Å, α = 98.77(3), β = 103.77(3), γ = 104.55(3)°; Z = 4). The coordination sphere is a square pyramid with the sulfur and phosphorus atoms as basal plane. Tc is situated out of this plane by 0.56 Å towards the nitrido ligand.     

Synthese eines Titana-Oxacyclohexanringes durch kontrollierte Ringöffnung von Tetrahydrofuran. Kristallstrukturen von [Ti(CH2)4O{Me2Si(NBut)2}]2, [TiCl{Me2Si(NBut)2}]3(μ3-O)(μ3-Cl) und [Li2(THF)3{Me2Si(NBut)2}]

Synthesis of a Titana-Oxacyclohexane Ring by Controlled Ring Opening of Tetrahydrofurane. Crystal Structures of [Ti(CH₂)₄O{Me₂Si(NBu^t)₂}]₂, [TiCl{Me₂Si(NBu^t)₂}]₃(μ₃-O)(μ₃-Cl), and [Li₂(THF)₃{Me₂Si(NBu^t)₂}] [TiCl₃(THF)₃] reacts with [(Bu^tNLi)₂SiMe₂]₂ in diethyl ether at –35 °C under redox disproportionation and formation of the yellow titana(IV)-oxacyclohexane complex [Ti(CH₂)₄O{Me₂Si(NBu^t)₂}]₂. According to the crystal structure analysis the titanium atoms are linked to form centrosymmetric dimers via the oxygen atoms of the Ti(CH₂)₄O six-membered rings, which are in chair conformation. Along with the nitrogen atoms of the chelating [Me₂Si(NBu^t)₂]^2– ligands the titanium atoms obtain a distorted trigonal-bipyramidal surrounding. While [TiCl{Me₂Si(NBu^t)₂}]₃(μ₃-O)(μ₃-Cl) with a cluster-like structure is obtained as a by-product. According to the crystal structure analysis of [Li₂(THF)₃ · {Me₂Si(NBu^t)₂}], which is involved in the synthesis reaction, the two lithium atoms are connected with both the nitrogen atoms of the t-butyl amide groups and bridged via an oxygen atom of one of the THF molecules.     

[{ReN(Me2PhP)(Et2dtc)Cl}2{ReN(Et22tc)2}2{SbCl3}2] — ein neuer vierkerniger Rheniumkomplex mit asymmetrischen Nitridobrücken

[{ReN(Me₂PhP)(Et₂dtc)Cl}₂{ReN(Et₂dtc)₂}₂{SbCl₃}₂] — a Novel Tetranuclear Rhenium Complex with Asymmetric Nitrido Bridges The reaction of [ReN(Et₂dtc)₂(Me2₂hP)] (Me₂PhP = dimethylphenylphosphine, Et₂dtc^‐ = diethyldithiocarbamate) with SbCl₃ in dichloromethane results in the formation of [{ReN(Me₂PhP)(Et2₂tc)Cl}₂{ReN(Et₂dtc)₂}₂{SbCl₃}₂]. A {Re≡N‐}₄ ring with asymmetric nitrido bridges is stabilised by the co‐ordination of SbCl₃ onto the chloro ligands and sulphur atoms of the dithiocarbamates. The compound decomposes upon heating in acetonitrile and the fragments of the tetrameric complex re‐arrange to form [ReN‐(Me₂PhP)(Et₂dtc)Cl]₄ and [ReN(Et₂dtc)₂]. The multinuclear rhenium compounds have been studied by X‐ray crystallography. The 8‐membered {Re≡N‐}₄ ring system in [{ReN(Me₂PhP)(Et₂dtc)Cl}2₂ReN(Et₂dtc)₂}₂{SbCl₃}₂] is almost planar, while that of [ReN(Me₂PhP)(Et₂dtc)Cl]₄ is clearly V‐shaped when viewed down either diagonal Re…Re axis. A dihedral angle of 47.88(2)° has been found between the contributing planes.     

Synthese und Kristallstrukturen der heteronuklearen Nitrido‐Komplexe [(Me2PhP)3(MeCN)ClRe≡N–MCl5] mit M = Sn und Zr

Synthesis and Structures of the Dinuclear Nitrido Complexes [(Me₂PhP)₃(MeCN)ClRe≡N–MCl₅] with M = Sn and Zr The water sensitive complexes [(Me₂PhP)₃(MeCN)ClRe≡N–MCl₅] (M = Sn ( 1 ) und Zr ( 2 )) are obtained in dichloromethane from [ReNCl₂(PMe₂Ph)₃] and the acetonitrile adducts of SnCl₄ or ZrCl₄. The compounds crystallize as dichloromethane solvate isotypically with [(Me₂PhP)₃(MeCN)ClRe≡N–TiCl₅] · CH₂Cl₂ in the space group P2₁/n. From toluene crystallize monoclinic crystals of 1 · MeCN · C₇H₈. In the diamagnetic complexes 1 and 2 an anion [MCl₅]^– coordinates to the nitrido ligand of the cationic complex [ReNCl(MeCN)(PMe₂Ph)₃]⁺. The resulting nitrido bridges Re≡N–M are almost linear and asymmetric with Re–N = 169.5 pm, Sn–N = 230.1 pm and Re–N–Sn = 164.5° for 1 and Re–N = 168.4 pm, Zr–N = 237.2 pm and Re–N–Zr = 165.6° for 2 . The phosphine ligands at the Re atom are in a meridional arrangement.     

Gemischtligandkomplexe des Technetiums. XV. Zur Reaktion von [TcNCl2(Me2PhP)3] mit Dialkyldithiocarbamaten und N,N-Dialkylthiocarbamoylbenzamidinen

Mixed-ligand Complexes of Technetium. XV. The Reaction of [TcNCl₂(Me₂PhP)₃] with Dialkyldithiocarbamates and N,N-Dialkylthio-carbamoylbenzamidines [TcN(Cl)(Me₂PhP)₂(Et₂dtc)], [TcN(Me₂PhP)(Et₂dtc)₂], and [TcN(Et₂dtc)₂] can be prepared by stepwise ligand exchange reactions starting from dichlorotris(dimethylphenylphosphine)nitridotechnetium(V), [TcNCl₂(Me₂PhP)₃], and diethyldithiocarbamate. In contrast to this, only one intermediate, [TcN(Cl)(Me₂PhP)₂(HEt₂tcb)], could be isolated during the reaction with N,N-Diethlthiocarbamoylbenzamidine, which yields the bis chelate [TcN(HEt₂tcb)₂]. [TcN(Me₂PhP)(Et₂dtc)₂] crystallizes in the monoclinic space group P2₁/c; a = 17.369(5) Å, b = 15.024(1) Å, c = 9.906(3) Å, β = 76.47(1)º, Z = 4. The phosphine is coordinated equatorially. The multiply bonded nitrogen ligand (Tc? N(1) 1.624(3) Å) strongly labilizes the trans positioned donor atom (distance Tc? S(4) 2.826(1) Å). [TcN(HEt₂tcb)₂] crystallizes in the triclinic space group P1 with a = 9.749(4) Å, b = 11.264(4) Å, c = 12.359(4) Å, α = 75.34(2)º, β = 79.69(2)º, γ = 87.55(2)º, Z = 2. The metal is five-coordinate with the nitrido donor atom occupying the apex of a square pyramid. It's basal plane is formed by the cis-coordinated chelate ligands. The technetium is situated over the basal plane by about 0.6 Å. The Tc?N distane was found to be 1.610(5) Å.     

Synthese und Struktur von [Re(NH)Cl2(PMe2Ph)3][TaCl6] und [(Me2PhP)3Cl2Re≡N]2VOCl2

Synthesis and Structure of [Re(NH)Cl₂(PMe₂Ph)₃][TaCl₆] and [(Me₂PhP)₃Cl₂Re≡N]₂VOCl₂ The products of the reaction of ReNCl₂(PMe₂Ph)₃ with TaCl₅ are dependent on the solvent. In CH₂Cl₂ the solvent protonates the nitrido ligand to yield [Re(NH)Cl₂(PMe₂Ph)₃][TaCl₆] as air-stable, reddish brown needles with the space group P2₁/n and a = 1213.8(3), b = 1358.0(2), c = 2165.9(4) pm, β = 92.88(1)°, Z = 4. The Re atom of the cation exhibits an octahedral coordination with the phosphine ligands in meridional arrangement. The imido ligand is in trans-position to a Cl atom with a distance Re–N = 170.4(4) pm. When the reaction is carried out in toluene the dinuclear nitrido complex [Re(NTaCl₅)Cl₂(PMe₂Ph)₃] is obtained instead. The reaction of ReNCl₂(PMe₂Ph)₃ with VCl₃(THF)₃ in toluene affords the threenuclear complex [Re₂N₂Cl₄(PMe₂Ph)₅]VCl₃, which upon crystallization at air gives air-stable, reddish-brown crystals of [(Me₂PhP)₃Cl₂ReN]₂VOCl₂. They crystallize in the monoclinic space group P2₁ with a = 1519.2(5), b = 1257.1(1), c = 1564.3(6) pm, β = 102.86(2)°, and Z = 2. The threenuclear complex shows an almost linear arrangement Re≡N–V–N≡Re with distances Re–N 171(2) pm and V–N of 209(2) pm.     

Synthese und Struktur von Komplexen mit Nitridobrücken zwischen Rhenium und Zink

Synthesis and Structure of Complexes with Nitrido Bridges between Rhenium and Zinc The reaction of [ReNCl₂(PMePh)₃] with ZnX₂ (X = Cl, Br) in CH₂Cl₂ yields the tetranuclear complexes [(Me₂PhP)₃X₂Re≡N–ZnX₂]₂. In case of the reaction with ZnBr₂ an exchange of the halogen atoms coordinated to the Re atom occurs. [(Me₂PhP)₃Cl₂Re≡N–ZnCl₂]₂ ( 1 ) crystallizes with one centrosymmetric tetranuclear complex in the triclinic unit cell. [(Me₂PhP)₃Br₂Re≡N–ZnBr₂]₂ ( 2 ) forms triclinic crystals with the composition 2 · 2 CH₂Cl₂. The centrosymmetric tetranuclear complexes exhibit analogous structures. Two complexes [ReNX₂(PMe₂Ph)₃] coordinate with the terminal nitrido ligands the Zn atoms of a central unit XZn(μ-X)₂ZnX. The resulting linear nitrido bridges Re≡N–Zn (Re–N–Zn = 178.4° ( 1 ) und 178.0° ( 2 )) are asymmetric with distances Re–N = 170 pm and Zn–N = 199 pm for 1 , and Re–N = 167 pm as well as Zn–N = 201 pm for 2 . The reaction of [ReNCl₂(PMe₂Ph)₃] with ZnI₂ in CH₂Cl₂ presumably first affords [(Me₂PhP)₃ClIRe≡N–ZnI₂]₂, which, however, in the course of crystallization decomposes to yield [(Me₂PhP)₃ClIRe≡N–ZnI₂(OPMe₂Ph)] ( 3 ). Of the two Cl atoms originally coordinated at the Re atom the one in cis position to the nitrido ligand is substituted by iodine. 3 forms monoclinic crystals with the space group P2₁/n. The distances in the linear nitrido bridge (Re–N–Zn = 171.5°) are Re–N = 167.9 pm and Zn–N = 204.9 pm. By the reaction of [ReNCl₂(PMe₂Ph)₃] with ZnX₂ (X = Cl, I) in THF the dinuclear complexes [(Me₂PhP)₃Cl₂Re≡N–ZnCl₂(THF)] ( 4 ) and [(Me₂PhP)₃ClIRe≡N–ZnI₂(THF)] ( 5 ) are obtained. They crystallize isotypically as 4 · THF or 5 · THF in the triclinic space group P1. Their nitrido bridges have the following parameters: Re–N–Zn = 175.2°, Re–N = 167.7 pm, and Zn–N = 202.1 pm for 4 , resp. Re–N–Zn = 174.7°, Re–N = 168.3 pm, and Zn–N = 201.2 pm for 5 .     

Reactions of [ReN(Cl)(Me2PhP)2(HEt2tcb)] with Lewis Acids. Synthesis,Characterization and Structures of [Re(NBBr3)Br2(Me2PhP)3], [Re(NGaCl3)Cl(Me2PhP)2(H2Et2tcb)][GaCl4] and [Re{NB(C6F5)3}Cl(Me2PhP)2(HEt2tcb)] (H2Et2tcb=N,N-diethylthiocarbamoylbenzamidine)

Reactions of [ReN(Cl)(Me₂PhP)₂(HEt₂tcb)] (HEt₂tcb⁻=N,N-diethylthiocarbamoylbenzamidinate, Me₂PhP=dimethylphenylphosphine) with Lewis acidic compounds such as BBr₃, (C₆F₅)₃B or gallium(III) chloride yield nitrogen-bridged binuclear complexes with covalent bonds between the nitrido ligand and boron or gallium. The reactions go along with activation of the transition metal centre which can lead to ligand re-arrangements and reactions with solvent molecules.The reaction with BBr₃ results in cleavage of the bonds to the chelating ligand. [Re(NBBr₃)Br₂(Me₂PhP)₃] was isolated as the only product with a nitrido bridge. The bis-chelate [ReN(HEt₂tcb)₂] was formed as a side-product.Upon formation of a nitrido bridge to GaCl₃ the first co-ordination sphere of rhenium is retained. The co-ordinated thiocarbamoylbenzamidinate, however, undergoes protonation and is bonded as a neutral, bidentate ligand in the product [Re(NGaCl₃)Cl(Me₂PhP)₂(H₂Et₂tcb)][GaCl₄].In [Re{NB(C₆F₅)₃}Cl(Me₂PhP)₂(HEt₂tcb)], which can be obtained in good yield from the reaction of [ReN(Cl)(Me₂PhP)₂(HEt₂tcb)] with (C₆F₅)₃B, the co-ordination environment of the metal remains essentially unchanged.X-ray structural studies on the products suggest that the strong structural trans influence of the terminal nitrido ligand in the starting complex decreases significantly as a consequence of the formation of the N–B/Ga bonds. The rhenium–nitrogen multiple bond distances, however, remain almost unchanged.     

Polysulfonylamine. XXXVII. Darstellung von Quecksilberdimesylamiden. Kristall- und Molekülstrukturen von Hg[N(SO2CH3)2]2, Hg[{N(SO2CH3)2}2(DMSO)2] und Hg[{N(SO2CH3)2}2(HMPA)]

Polysulfonyl Amines. XXXVII. Preparation of Mercury Dimesylamides. Crystal and Molecular Structures of Hg[N(SO₂CH₃)₂]₂, Hg[{N(SO₂CH₃)₂}₂(DMSO)₂], and Hg[{N(SO₂CH₃)₂}₂(HMPA)] Hg[N(SO₂CH₃)₂]₂ ( 1 ) and Hg₂[N(SO₂CH₃)₂]₂ ( 2 a ) are formed as colourless, sparingly soluble precipitates when solutions of Hg(NO₃)₂ or Hg₂(NO₃)₂ in dilute nitric acid are added to an aqueous HN(SO₂CH₃)₂ solution. By a similar reaction, Hg₂[N(SO₂C₆H₄ ? Cl? 4)₂]₂ is obtained. 1 forms isolable complexes of composition Hg[N(SO₂CH₃)₂]₂ · 2 L with L = dimethyl sulfoxide (complex 3 a ), acetonitrile, dimethyl formamide, pyridine or 1,10-phenanthroline and a (1/1) complex Hg[N(SO₂CH₃)₂]₂ · HMPA ( 4 ) with hexamethyl phosphoramide. Attempted complexation of 2 a with some of these ligands induced formation of Hg⁰ and the corresponding Hg^II complexes. Crystallographic data (at -95°C) are for 1: space group 14₁/a, a = 990.7(2), c = 2897.7(8) pm, V = 2.844 nm³, Z = 8, D_x = 2.545Mgm^?3; for 4a: space group P1 , a = 767.8(2), b = 859.2(2), c = 925.2(2)pm α = 68.44(2), β = 86.68(2), γ = 76.24(2)°, V = 0.551nm³, Z = 1, D_x = 2.113 Mgm^?3; for 4: space group P2₁/c, a = 1041.3(3), b = 1545.4(3), c = 1542.5(3) pm, β = 100.30(2)°, V = 2.474nm³, Z = 4, D_x = 1.944Mgm³. The three compounds form molecular crystals. The molecular structures contain a linear or approximately linear, covalent NHgN moiety; the Hg? N distances and N? Hg? N angles are 206.7(4) pm and 176.3(2)° for 1, 207.2(2) pm and 180.0° for 3a, 205.7(4)/206.7(4) pm and 170.5(1)° for 4. In the complexes 3a and 4, the 0-ligands are bonded to the Hg atoms perpendicularly to the N? Hg? N axes, leading in 3a to a square-planar trans-(N₂O₂) coordination with Hg? 0 261.2(2) pm and N? Hg? O 92.3(1)/87.7(1)°, in 4 to a slightly distorted T-shaped (N₂O) geometry with Hg? 0 246.2(4)pm and N? Hg? 0 96.7(1)/92.0(1)°. In all three structures, the primary coordination is extended to a severely distorted (N₂O₄) hexacoordination by the appropriate number of secondary, inter- and/or intramolecular Hg…?0 inter-actions (0 atoms from sulfonyl groups, Hg…?O distances in the range 280—300pm). The intramolecular Hg…?O interactions give rise to nearly planar four-membered [HgNSO] rings. The molecule of 1 has a two-fold axis through the bisector of the N? Hg? N angle, the molecule of 3a an inversion center at the Hg atom. The molecule of 4 has no symmetry.     

Triethylphosphanimin-Komplexe der Acetate von Kupfer(II) und Zink. Kristallstrukturen von [Zn(O2C–CH3)2(HNPEt3)], [Cu5(O2C–CH3)10(HNPEt3)2] und [Cu(O2C–CH3)2(HNPEt3)2]

Triethylphosphanimine Complexes of the Acetates of Copper(II) and Zinc. Crystal Structures of [Zn(O₂C–CH₃)₂(HNPEt₃)], [Cu₅(O₂C–CH₃)₁₀(HNPEt₃)₂], and [Cu(O₂C–CH₃)₂(HNPEt₃)₂] The title compounds originate from the anhydrous acetates of zinc and copper(II) with trimethylsilyl-triethylphosphanimine, Me₃SiNPEt₃, in the presence of water in dichloromethane. They form colourless ( 1 ), bluish-green ( 2 ), and blue ( 3 ), respectively, single crystals, which were characterized by IR spectroscopy and by crystal structure analyses. [Zn(O₂C–CH₃)₂(HNPEt₃)] ( 1 ): Space group P 4 2₁c, Z = 8, lattice dimensions at –83 °C: a = b = 1709.6(2), c = 982.4(1) pm, R = 0.0551. 1 has a polymeric chain structure in which the zinc atoms are μ₂-bridged via the oxygen atoms of one of the two acetato groups, while the second acetato group and the phosphanimine are bonded terminally. [Cu₅(O₂C–CH₃)₁₀(HNPEt₃)₂]( 2 · 4 CH₂Cl₂): Space group P2₁/c, Z = 8, lattice dimensions at –80 °C: a = 1761.18(13), b = 4074.5(2), c = 1733.34(15) pm, β = 91.383(10)°, R = 0.0413. 2 consists of the two structural units [Cu₂(O₂C–CH₃)₄] and [Cu₃(O₂C–CH₃)₆(HNPEt₃)₂], which are connected via two of the acetato groups of the Cu₃-unit along the crystallographic a-axis to form three crystallographically independent polymeric strands. [Cu(O₂C–CH₃)₂(HNPEt₃)₂] ( 3 ): Space group P2₁/n, Z = 2, lattice dimensions at 20 °C: a = 695.49(8), b = 1217.85(10), c = 1380.05(7) pm, β = 96.451(7)°, R = 0.0291. 3 forms monomeric, centrosymmetric molecules with a square planar environment at the Cu atoms.     

Synthese,Struktur und Eigenschaften der Komplexe [(H2O)Cl4Os≡N‐IrCl(C5Me5)(AsPh3)], [(Ph3Sb)Cl4Os≡N‐IrCl(C5Me5)(SbPh3)], [(Ph3Sb)2Cl3Os≡N‐IrCl(COD)] und [{(Me2PhP)2(CO)Cl2Re≡N}2ReNCl2(PMe2Ph)]

Synthesis, Crystal Structure, and Properties of the Complexes [(H₂O)Cl₄Os≡N‐IrCl(C₅Me₅)(AsPh₃)], [(Ph₃Sb)Cl₄Os≡N‐IrCl(C₅Me₅)(SbPh₃)], [(Ph₃Sb)₂Cl₃Os≡N‐IrCl(COD)] and [{(Me₂PhP)₂(CO)Cl₂Re≡N}₂ReNCl₂(PMe₂Ph)] The dinuclear complexes [(H₂O)Cl₄Os≡N‐IrCl(C₅Me₅)(AsPh₃)]·H₂O ( 1 ·H₂O), [(Ph₃Sb)Cl₄Os≡N‐IrCl(C₅Me₅)(SbPh₃)] ( 2 ), and [(Ph₃Sb)₂Cl₃Os≡N‐IrCl(COD)] ( 3 ) result from the reaction of the nitrido complexes [(Ph₃As)₂OsNCl₃] and [(Ph₃Sb)₂OsNCl₃] with the iridium compounds [IrCl₂(C₅Me₅)]₂ and [IrCl(COD)]₂ in dichloromethane. 1 crystallizes as 1 ·H₂O in form of green platelets in the monoclinic space group Cm and a = 1105.53(6); b = 1486.76(9); c = 2024.88(10) pm, β = 97.191(4)°, Z = 4. The formation of 1 in air involves a ligand exchange, and the coordination of a water molecule in trans position to the Os‐N triple bond. The resulting complex fragments [(H₂O)Cl₄Os≡N] and [IrCl(C₅Me₅)(AsPh₃)] are connected by an asymmetric nitrido bridge Os≡N‐Ir. The nitrido bridge is characterised by an Os‐N‐Ir bond angle of 173.7(7)°, and distances Os‐N = 168(1) pm and Ir‐N = 191(1) pm. 2 crystallizes in clumped together brown platelets with the space group and a = 1023.3(3), b = 1476.2(3), c = 1872.5(6) pm, α = 74.60(2), β = 73.84(2), γ = 76.19(2)°, Z = 2. In 2 the asymmetric nitrido bridge Os≡N‐Ir joins the two complex fragments [(Ph₃Sb)Cl₄Os≡N] and [IrCl(C₅Me₅)(SbPh₃)], which are formed by a ligand exchange reaction. 3 forms dark green crystals with the triclinic space group and a = 1079.4(1), b = 1172.3(1), c = 1696.7(2) pm, α = 101.192(9),β = 92.70(1), γ = 92.61(1)°, Z = 2. The distances in the almost linear nitrido bridge (Os≡N‐Ir = 175.3(7)°) are Os‐N = 171(1) pm and Ir‐N = 183(1) pm. The reaction of [ReNCl₂(PMe₂Ph)₃] with [Mo(CO)₃(NCMe)₃] unexpectedly affords the trinuclear complex [{(Me₂PhP)₂(OC)Cl₂Re≡N}₂ReNCl₂(PMe₂Ph)] ( 4 ) as the main product. It forms triclinic brown crystals with the composition 4 ·2THF and the space group (a = 1382.70(7), b = 1498.58(7), c = 1760.4(1) pm, α = 99.780(7), β = 99.920(7), γ = 114.064(6)°, Z = 2). In the trinuclear complex, the central fragment, [ReNCl₂(PMe₂Ph)] is joined in trans position to two nitrido complexes [(Me₂PhP)₂(CO)Cl₂Re≡N], giving an almost linear Re≡N‐Re‐N≡Re arrangement. The bond angles and distances in the nitrido bridges are Re‐N‐Re = 167.8(3)°, Re‐N = 171.1(8) pm and 204.2(8) pm; and Re‐N‐Re = 168.1(4)°, Re‐N = 170.9(9) and 203.5(9) pm respectively. As expected, the Re‐N bond length to the terminal nitrido ligand on the central Re atom is much shorter at 161.2(9) pm than the triple bonds of the asymmetric bridges.     

Binary salt of a palladium(II) complex with (phosphonomethyl)phosphonic (medronic) acid comprising `handbell‐like' [Pd{μ‐CH2(PO3)2}]3 units

The asymmetric unit of the title compound, dipotassium bis[hexaaquanickel(II)] tris(μ₂‐methylenediphosphonato)tripalladium(II) hexahydrate, K₂[Ni(H₂O)₆]₂[Pd₃{CH₂(PO₃)₂}₃]·6H₂O, consists of half a {[Pd{CH₂(PO₃)₂}]₃}⁶⁻ anion [one Pd atom (4e) and a methylene C atom (4e) occupy positions on a twofold axis] in a rare `handbell‐like' arrangement, with K⁺ and [Ni(H₂O)₆]²⁺ cations to form the neutral complex, completed by three solvent water molecules. The {[Pd{CH₂(PO₃)₂}]₃}⁶⁻ units exhibit close Pd...Pd separations of 3.0469 (4) Å and are packed via intermolecular C—H...Pd hydrogen bonds. The [KO₉] and [NiO₆] units are assembled into sheets coplanar with (011) and stacked along the [100] direction. Within these sheets there are [K₄Ni₄O₈] and [K₂Ni₂O₄] loops. Successive alternation of the sheets and [Pd{CH₂(PO₃)₂}]₃ units parallel to [001] produces the three‐dimensional packing, which is also supported by a dense network of hydrogen bonds involving the solvent water molecules.     

Synthese und Struktur der Nitrido‐Komplexe (PPh4)2[(O3Os≡N)2MCl2](M = Pd und Pt) und [{(Me2PhP)3Cl2Re≡N}2PdCl2]

Synthesis and Structure of the Nitrido Complexes (PPh₄)₂[(O₃Os≡N)₂ MCl₂] (M = Pd und Pt) and [{(Me₂PhP)₃Cl₂Re≡N}₂PdCl₂] The threenuclear complexes (PPh₄)₂[(O₃Os≡N)₂MCl₂] (M = Pd ( 1a ) and Pt ( 1b )) are obtained by the reaction of (PPh₄) [OsO₃N] with [MCl₂(NCC₆H₅)₂] (M = Pd and Pt) in form of orange red ( 1a ) or red brown ( 1b ) crystals. The compounds crystallize isotypically in the monoclinic space group P2₁/n with a = 1052.35(6), b = 1376.70(6), c = 1607.3(1) pm, β = 94.669(7)°, and Z = 2 for 1a and a = 1053.27(7), b = 1371.6(1), c = 1615.9(1) pm, β = 94.557(7)°, and Z = 2 for 1b . In the centrosymmetric complex anions [(O₃O≡N)₂MCl₂]^2— a linear MCl₂ moiety is connected in trans arrangement with two complexes [O₃Os≡N]^— via asymmetric nitrido bridges Os≡N‐M. For the M²⁺ cations such results a square‐planar coordination MCl₂N₂. The virtually linear nitrido bridges are characterized by distances Os‐N = 167.5 pm ( 1a ) and 164.2 pm ( 1b ) as well as Pd‐N = 196.2 pm and Pt‐N = 197.8 pm. The reaction of ReNCl₂(PMe₂Ph)₃ with PdCl₂(NCC₆H₅)₂ in CH₂Cl₂ yields red crystals of the heterometallic complex [{(Me₂PhP)₃Cl₂Re≡N}₂PdCl₂] ( 2 ). It crystallizes as 2 · 2 CH₂Cl₂ in the monoclinic space group C2/c with a = 2138.3(5); b = 1260.9(3); c = 2375.6(2) pm; β = 96.09(1)° and Z = 4. In the threenuclear complex [{(Me₂PhP)₃Cl₂Re≡N}₂PdCl₂] with the symmetry C_i the coordination of the Pd²⁺ cation of the central PdCl₂ unit is completed by two nitrido bridges Re≡N‐Pd to complexes (Me₂PhP)₃Cl₂Re≡N forming a square‐planar arrangement. The distances in the linear nitrido bridges are Re‐N = 170.2 pm and Pd‐N = 197.1 pm.