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.     

[Tc(NBCl2Ph)Cl2(Me2PhP)3] und [Tc(NBH3)Cl2(Me2PhP)3] – die ersten Technetium‐Komplexe mit Nitridobrücken zwischen Technetium und Bor

[Tc(NBCl₂Ph)Cl₂(Me₂PhP)₃] and [Tc(NBH₃)Cl₂(Me₂PhP)₃] – the First Technetium Complexes with Nitrido Bridges between Technetium and Boron [TcNCl₂(Me₂PhP)₃] reacts with BCl₂Ph or BH₃ · THF at low temperatures under formation of complexes containing a nitrido bridge between technetium and boron. The compounds are instable and decompose at room temperature under cleavage of the N–B bonds. The pale‐purple [Tc(NBCl₂Ph)Cl₂(Me₂PhP)₃] crystallizes in the orthorhombic space group Fdd2. The Tc≡N bond is only slightly lengthened by the formation of the N–B bond of 1.564(4) Å. However, a considerable lengthening of the Tc–Cl bond in trans position to the nitrido ligand is observed which can be attributed to an decreasing of the structural trans influence of the nitrido moiety. A similar structural feature can be found in [Tc(NBH₃)Cl₂(Me₂PhP)₃] which is the first structurally characterized transition metal complex containing a nitrido bridge to unsubstituted borane.     

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.     

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. V. Die Bildung von Nitrenkomplexen durch Kondensation von Aceton an koordinierten Nitridoliganden. Darstellung und Strukturen von fac-[Re{NC(CH3)2CH2C(O)CH3}X3(Me2PhP)2]-Komplexen (X = Cl,Br)

Mixed-ligand Complexes of Rhenium. V. The Formation of Nitrene Complexes by Condensation of Acetone at Coordinated Nitrido Ligands. Syntheses and Structures of fac-[Re{NC(CH₃)₂CH₂C(O)CH₃}X₃(Me₂PhP)₂] Complexes (X = Cl, Br) The reaction of rhenium(V)-mixed-ligand complexes of the general formula [ReN(Cl)(Me₂PhP)₂(R₂tcb)] (HR₂tcb = N? (N,N-dialkylthiocarbamoyl)benzamidine) with HCl or HBr in acetone initializes a condensation of the solvent and results in nitrene-like compounds as a consequence of a nucleophilic attack of the coordinated nitrido ligand on the condensed acetone. The chelate ligands are removed during this reaction and complexes of the type fac-[Re{NC(CH₃)₂CH₂C(O)CH₃}X₃(Me₂PhP)₂] (X = Cl, Br) are formed. fac-[Re{NC(CH₃)₂CH₂C(O)CH₃}Cl₃(Me₂PhP)₂] crystallizes triclinic in the space group P1, a = 8.575(4); b = 9.088(3); c = 18.389(9) Å; α = 75.67(3)°, β = 85.30(3)°, γ = 70.58(4)°; Z = 2. A final R value of 0.031 was obtained on the basis of 6011 independent reflections with I ≥ 2σ(I). Rhenium is coordinated in a distorted octahedral environment with the three chloro ligands in facial positions. The rhenium-nitrogen bond (1,68(1) Å) is only slightly longer than typical Re? N bonding distances in nitrido complexes. fac-[Re{NC(CH₃)₂CH₂C(O)CH₃}Br₃(Me₂PhP)₂] is isomorphous with the chloro complex. Triclinic cell with a = 8.625(4); b = 9.198(3); c = 18.581(5) Å; α = 75.62(3)°, β = 85.40(3)°, γ = 70.91(3)°; Z = 2. The R value converged at 0.049 on the basis of 3644 independent reflections with I ≥ 2σ(I). fac-[Re{NC(CH₃)₂CH₂C(O)CH₃}Cl₃(Me₂PhP)₂] as well as fac-[Re{NC(CH₃)₂CH₂C(O)CH₃}Br₃(Me₂PhP)₂] crystallizes in the noncentrosymmetric space group P1.     

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.     

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.     

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)°.     

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 der Komplexe [(Me2PhP)3Cl2Re≡N‐RuCl2(C6H6)] und [(Me2PhP)3Cl2Re≡N‐RhCl(COD)]

Synthesis and Crystal Structure of the Complexes [(Me₂PhP)₃Cl₂Re≡N‐RuCl₂(C₆H₆)] and [(Me₂PhP)₃Cl₂Re≡N‐RhCl(COD)] The heteronuclear complex [(Me₂PhP)₃Cl₂Re≡N‐RuCl₂(C₆H₆)] ( 1 ) is obtained by the reaction of [ReNCl₂(PMe₂Ph)₃] with [RuCl₂(C₆H₆)]₂ in C₆H₅CN in form of red crystals with the composition 1 ·C₆H₅CN crystallizing in the monoclinic space group P2₁/c with a =1149.77(8), b = 3085.9(3), c = 1172.1(1) pm, β = 104.766(9)° and Z = 4. In the dinuclear complex the complex fragment [RuCl₂(C₆H₆)] is connected by an asymmetric nitrido bridge with the nitrido complex [ReNCl₂(PMe₂Ph)₃]. The nitrido bridge is characterised by a bond angle Re‐N‐Ru of 170.6(3)° and distances Re‐N = 170.2(5) and Ru‐N = 199.0(5) pm. The reaction of [ReNCl₂(PMe₂Ph)₃] with [RhCl(COD)]₂ in benzonitrile yields orange crystals of [(Me₂PhP)₃Cl₂Re≡N‐RhCl(COD)] ( 2 ) with the space group P2₁/c and a = 1522.3(2), b = 1274.85(4), c = 1921.2(2) pm, β = 106.759(7)° and Z = 4. The monovalent Rh atom exhibits a square planar coordination with the two π‐bonds of the cycloocta‐1, 5‐diene occupying cis positions. The distances in the almost linear nitrido bridge (Re‐N‐Rh = 174.8(4)°>) are Re‐N = 172.2(6) pm and Rh‐N = 195.6(6) pm.     

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 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.     

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 und Struktur von [(Me2PhP)3Cl2ReN]2NbCl4 und [Re3N3Cl5(PMe2Ph)6][NbCl6]

Synthesis and Structure of [(Me₂PhP)₃Cl₂ReN]₂NbCl₄ and [Re₃N₃Cl₅(PMe₂Ph)₆][NbCl₆] The reaction of ReNCl₂(PMe₂Ph)₃ with NbCl₅ in toluene yields the trinuclear complexes [(Me₂PhP)₃Cl₂ReN]₂‐ NbCl₄ (1) and [Re₃N₃Cl₅(PMe₂Ph)₆][NbCl₆] ( 2 ). 1 forms triclinic crystals with the composition 1 · 2 C₇H₈ (P 1, a = 1074.5(1), b = 1289.1(2), c = 1299.3(2) pm, α = 85.25(2)°, β = 81.04(2)°, γ = 86.02(1)°, Z = 1). In the centrosymmetric compound 1 two complexes ReNCl₂(PMe₂Ph)₃ coordinate with their nitrido ligands a square planar, central unit NbCl₄ to form an almost linear arrangement Re≡N–Nb–N≡Re. The length of the Re–N triple bonds is 172,2 pm, and the Nb–N distances of 216.0 pm correspond to coordinative single bonds. 2 forms orthorhombic crystals with the space group P2₁2₁2₁ and a = 1286.0(1), b = 2109.2(4), c = 2436.2(3) pm, Z = 4. The three Re atoms are located at the corners of a triangle. They are connected by two asymmetric nitrido bridges and two asymmetric chloro bridges. The weakly bent nitrido bridges (Re–N–Re = 152° and 157°) are characterized by Re–N distances of 169 und 207 pm as well as 171 and 207 pm. Re1, in addition, binds a terminal nitrido ligand with Re1–N1 = 166 pm.     

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.     

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.     

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.     

Synthese und Struktur von [(Me2PhP)3Cl2ReN]2ReCl4, [(Me2PhP)3Cl2ReN]2ReCl4 · 2 SbCl3 und [Re(NH)Cl2(PMe2Ph)3][SbCl6]

Synthesis and Structure of [(Me₂PhP)₃Cl₂ReN]₂ReCl₄, [(Me₂PhP)₃Cl₂ReN]₂ReCl₄ · 2 SbCl₃ and [Re(NH)Cl₂(PMe₂Ph)₃][SbCl₆] The reaction of ReNCl₂(PMePh)₃ with SbCl₅ in toluene yields the trinuclear complex [(Me₂PhP)₃Cl₂Re≡N]₂ReCl₄ · 2 SbCl₃ ( 1 · 2 SbCl₃). It forms triclinic crystals with the composition 1 · 2 SbCl₃, as well as monoclinic crystals 1 · 2 SbCl₃ · 4 C₇H₈. The monoclinic crystals with the space group P2₁/c, and a = 1212.3(2), b = 2098.5(4), c = 1827.7(3) pm, β = 95.51(1)°, Z = 2, have been used for a crystal structure determination. In the centrosymmetric complex 1 two complexes ReNCl₂(PMe₂Ph)₃ coordinate with their nitrido ligands a square planar, central unit ReCl₄. The SbCl₃ molecules are coordinated by chlorine bridges to Cl atoms of 1 , and, in addition, connect the complexes 1 with each other. The SbCl₃ free compound 1 is obtained in good yield by the reaction of ReNCl₂(PMePh)₃ with ReCl₄(NCEt)₂. It crystallizes in the triclinic space group P1 with a = 1037.7(3), b = 1153.0(2), c = 1393.8(3) pm, α = 72.31(2)°, β = 74.06(2)°, γ = 67.94(2)°, and Z = 1. The bond lengths of the Re–N triple bonds are 172 pm in 1 and 170 pm in 1 · 2 SbCl₃. By the reaction of ReNCl₂(PMePh)₃ with SbCl₅ in CH₂Cl₂ the solvent is decomposed forming HCl which protonates the nitrido ligand to afford the imido complex [Re(NH)Cl₂(PMe₂Ph)₃][SbCl₆] ( 2 ) crystallizing in the monoclinic space group P2₁/n with a = 1221.4(2), b = 1358.6(2), c = 2177.3(1) pm, β = 92,72(1)° and Z = 4. The Re–N distance in the almost linear unit Re≡N–H is 169,1 pm.     

Darstellung und Kristallstrukturen von (Ph3PNPPh3)2[Re2Br10] und (Ph4P)[Re2Br9]

Synthesis and Crystal Structures of (Ph₃PNPPh₃)₂[Re₂Br₁₀] and (Ph₄P)[Re₂Br₉] Depending on the molar ratio by reaction of [n-Bu₄N]₂[ReBr₆] with the Lewis acid BBr₃ in dichloromethane the bioctahedral complexes [n-Bu₄N]₂[Re₂Br₁₀] and [n-Bu₄N][Re₂Br₉] are formed. The X-ray structure determination on (Ph₃PNPPh₃)₂[Re₂Br₁₀] (monoclinic, space group C 2/c, a = 20.007(4), b = 15.456(5), c = 24.695(4) Å, β = 107.53(2)°, Z = 4) reveals a centrosymmetric edge-sharing complex anion with approximate D_2h symmetry and mean terminal and bridging Re–Br bond lengths of 2.453 (equatorial), 2.482 (axial) and 2.591 Å, respectively, and a Re–Re distance of 3.880 Å. (Ph₄P)[Re₂Br₉] (triclinic, space group P 1, a = 11.062(2), b = 12.430(3), c = 13.163(5) Å, α = 72.94(2), β = 68.47(2), γ = 82.09(2)°, Z = 2) contains a confacial bioctahedral anion with nearly D_3h symmetry and mean terminal and bridging Re–Br distances of 2.460 and 2.536 Å, respectively, and a Re–Re distance of 2.780 Å.     

Synthese und Struktur von (Me2PhP)3Cl2Re≡N–ReCl4(PMe2Ph), einem gemischtvalenten Zweikernkomplex mit einer Nitridobrücke zwischen ReV und ReIV

Synthesis and Structure of (Me₂PhP)₃Cl₂Re≡N–ReCl₄(PMe₂Ph), a Mixed Valent Dinuclear Complex with a Nitrido Bridge between Re^V and Re^IV The nitrido complex (Me₂PhP)₃Cl₂Re≡N–ReCl₄(PMe₂Ph) results from the reaction of ReNCl₂(PMe₂Ph)₃ with GeCl₄ in toluene. The mixed valent dinuclear complex is paramagnetic with μ_eff = 1.96 B. M. at 300 K. It crystallizes with one solvate molecule as red crystals (Me₂PhP)₃Cl₂Re≡N–ReCl₄(PMe₂Ph) · C₇H₈ with the space group P 1 and a = 1075.4(6), b = 1330.5(6), c = 1745.3(11) pm, α = 101.20(3), β = 105.88(3), γ = 94.23(3)°, Z = 2. In the dinuclear complex one molecule ReNCl₂(PMe₂Ph)₃ coordinates with its nitrido ligand to a fragment ReCl₄(PMe₂Ph). The resulting nitrido bridge is asymmetrical with distances Re–N of 170.6(6) and 205.5(6) pm, and a bond angle Re1–N–Re2 = 174.6(3)°.