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 .     

Synthese und Struktur von dreikernigen Heterometall-Komplexen mit Nitridobrücken zwischen Re und Sn

Synthesis and Structure of Threenuclear Heterometallic Complexes with Nitrido Bridges between Re and Sn The threenuclear heterometallic complex [(Me₂PhP)₂ClRe(μ-Cl)N]₂SnCl₄ results from the reaction of ReNCl₂(PMe₂Ph)₃ with SnCl₄ in CH₂Cl₂. The brown, air-sensitive complex is diamagnetic. It crystallizes with two solvate molecules as [(Me₂PhP)₂ClRe(μ-Cl)N]₂SnCl₄ · 2 CH₂Cl₂ in the space group P 1 with a = 1189.1(2), b = 1262.3(2), c = 1776.7(3) pm, α = 86.04(2), β = 89.27(2), γ = 72.75(1)°, Z = 2. In the threenuclear complex two fragments (Me₂PhP)₂ClReN, which are connected by two Cl bridges, coordinate with their nitrido ligands one SnCl₄ molecule. The two resulting nitrido bridges complete the coordination of the Sn atom to a distorted octahedron with a cis arrangement of the N atoms. The bent nitrido bridges (Re–N–Sn = 155) are asymmetrical with distances Re–N = 168 pm and Sn–N = 225 pm. An incomplete exclusion of water during the synthesis leads to the formation of [(Me₂PhP)₃ClRe(μ-Cl)N]Sn₂(OH)Cl₇ · 2 CH₂Cl₂ in form of air-stable, red-violett crystals (P 1, a = 1074.1(2), b = 1251.1(3), c = 1685.0(1) pm, α = 99.61(2), β = 91.49(2), γ = 92.69(2)°, Z = 2). In the diamagnetic complex one molecule ReNCl₂(PMe₂Ph)₃ is coordinated by the nitrido ligand and one Cl bridge to the Sn atoms of a unit Sn₂(OH)Cl₇. In this unit the two Sn atoms are connected by one Cl and one OH bridge. The distances in the almost linear nitrido bridge (Re–N–Sn = 164.6) are Re–N = 170.5 pm and Sn–N = 219.8 pm.     

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.     

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.     

Synthese,Struktur und Eigenschaften der Komplexe [(Me2PhP)3Cl2Re≡N‐IrCl2(C5Me5)], [(Me2PhP)3Cl2Re≡N‐IrCl(COD)], [PPh4][O3Os≡N‐IrCl2(C5Me5)] und [PPh4][O3Os≡N‐IrCl(COD)] mit Nitridobrücken Re≡N‐Ir und Os≡N‐Ir

Synthesis and Crystal Structures of the Complexes [(Me₂PhP)₃Cl₂Re≡N‐IrCl₂(C₅Me₅)], [(Me₂PhP)₃Cl₂Re≡N‐IrCl(COD)], [PPh₄][O₃Os≡N‐IrCl₂(C₅Me₅)], and [PPh₄][O₃Os≡N‐IrCl(COD)] with Nitrido bridges Re≡N‐Ir and Os≡N‐Ir The heteronuclear complexes [(Me₂PhP)₃Cl₂Re≡N‐IrCl₂(C₅Me₅)] ( 1 ), [(Me₂PhP)₃Cl₂Re≡N‐IrCl(COD)] ( 2 ), [PPh₄][O₃Os≡N‐IrCl₂(C₅Me₅)] ( 3 ) and [PPh₄][O₃Os≡N‐IrCl(COD)] ( 4 ) were obtained by the reaction of the nitrido complexes [ReNCl₂(PMe₂Ph)₃] and [OsO₃N]^— with the iridium compounds [IrCl₂(C₅Me₅)]₂ and [IrCl(COD)]₂ in benzonitrile. 1 forms red crystals with the composition 1 ·C₆H₅CN in the monoclinic space group P2₁/c and a = 1264.7(2); b = 1945.3(2); c = 1835.4(1) pm, β = 90.35(1)°, Z = 4. The complex fragment [IrCl₂(C₅Me₅)] in the dinuclear complex is connected by an asymmetric nitrido bridge Re≡N‐Ir to the nitrido complex [ReNCl₂(PMe₂Ph)₃]. The nitrido bridge is characterized by a Re‐N‐Ir bond angle of 179.4(2)° and distances Re‐N = 170.9(4) pm and Ir‐N = 203.3(4) pm. 2 forms brownish red, triclinic crystals with the space group P1¯ and a = 1076.6(2), b = 1373.2(2), c = 1452.4(1) pm, α = 107.513(8), β = 101.843(9), γ = 110.04(1)°, Z = 2. The nitrido bridge to the complex fragment [IrCl(COD)] has a Re‐N‐Ir bond angle of 173, 8(4)° and distances Re‐N = 170, 4(8) pm and Ir‐N = 196, 2(8) pm. 3 crystallizes as monoclinic red crystals in the space group P2₁/n and a = 1449.9(2), b = 906.74(4), c = 2628.9(5) pm, β = 103.50(1)°, Z = 4. The nitrido bridge Os≡N‐Ir is slightly bent (Os‐N‐Ir = 165.0(3)°). The distances are Os‐N = 168.3(5) pm and Ir‐N = 201.9(5) pm. 4 forms dark brown, orthorhombic crystals with the space group P2₁2₁2₁ and a = 704.35(2), b = 1228.17(6), c = 3442.0(4) pm, Z = 4. The distances in the slightly bent nitrido bridge (Os‐N‐Ir = 161.8(4)°) are Os‐N = 169.3(7) pm und Ir‐N = 197.8(7) pm.     

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.     

[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.     

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 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. 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 Kristallstruktur von Rb8[P4N6(NH)4](NH2)2 mit dem adamantanartigen Anion [P4N6(NH)4]6−

Synthesis and Crystal Structure of Rb₈[P₄N₆(NH)₄](NH₂)₂ with the Adamantane-like Anion [P₄N₆(NH)₄]^6? RbNH₂ reacts with P₃N₅ (molar ratio 6:1) at 400°C within 5 d to colourless Rb₈[P₄N₆(NH)₄](NH₂)₂. Suitable crystals for a X-ray structure determination were obtained: The compound contains adamantane-like molecular anions [P₄N₆(NH)₄]^6?. Their centres of gravity are arranged in a distorted hexagonal primitive array. All trigonal prisms of this array contain one amide ion. Rubidium ions connect the anions irregularly.     

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.     

Nitrido-Sodalithe. I Synthese,Struktur und Eigenschaften von Zn7–xH2x[P12N24]Cl2 mit 0 ⩽ x ⩽ 3

Nitrido Sodalites. I Synthesis, Crystal Structure, and Properties of Zn_7–xH_2x [P₁₂N₂₄]Cl₂ with 0 ? x ? 3 The nitrido sodalites Zn_7–xH_2x[P₁₂N₂₄]Cl₂ with 0 ? x ? 3 are obtained by heterogeneous pressure-ammonolysis of P₃N₅ at presence of ZnCl₂ (T = 650°C). These compounds are available too by reaction of ZnCl₂, (PNCl₂)₃, and NH₄Cl at 700°C. The crystal structures of four representatives of the above mentioned compounds have been refined by the Rietveld full-profile technique using X-ray powder diffractometer data (I4 3m, a = 821.61(4) to 824.21(1) pm, Z = 1). In the solid a three-dimensional framework of corner-sharing PN₄-tetrahedra occurs (P? N: 163.6 pm, P? N? P: 125.6°, mean values) which is isosteric with the sodalite type of structure. In the center of the β-cages Cl^? ions have been found, which are tetrahedrally coordinated by Zn²⁺ ions. The Zn²⁺ ions are statistically disordered. According to the phase-width observed (0 ? x ? 3) the Zn²⁺ ions may be partially replaced each by two hydrogen atoms which on the other hand are covalently bonded to nitrogen atoms of the P? N framework. The IR-spectra of these compounds show characteristic vibrations.     

Synthese von Nitrenkomplexen mit N-Trimethylsilylanilin. II. Charakterisierung und Kristallstruktur der Rhenium(V)-phenylnitren-Komplexe mer-[Re(NPh)Cl3(NH2Ph)(Ph3P)] und trans-[Re(NPh)(OMe)Cl2(Ph3P)2]

Synthesis of Phenylnitrene Complexes with N-Trimethylsilylaniline. II. Characterization and Crystal Structure of the Rhenium(V) Complexes mer-[Re(NPh)Cl₃(NH₂Ph)(Ph₃P)] and trans-[Re(NPh)(OMe)Cl₂(Ph₃P)₂] Reaction of [ReOCl₃(Ph₃P)₂] with N-trimethylsilylaniline yields mer-[Re(NPh)Cl₃(Ph₃P)₂], which reacts under air with excess of N-trimethylsilylaniline to form [Re(NPh)Cl₃ · (NH₂Ph)(Ph₃P)]. Crystallization from CH₂Cl₂/MeOH affords [Re(NPh)(OMe)Cl₂(Ph₃P)₂] as an additional product. [Re(NPh)Cl₃(NH₂Ph)(Ph₃P)] crystallizes in the monoclinic space group P2₁/n with a = 1 192.3(3); b = 1 918.9(3); c = 1 266.3(3) pm; β = 101.71(1)°; Z = 4. The rhenium atom has a distorted octahedral environment with the Cl atoms in meridional positions. The phenyl nitrene ligand is coordinated with an almost linear arrangement Re? N1? C40 = 166.8(6)° and with a bond distance Re?N = 170.5(6) pm. [Re(NPh)(OMe)Cl₂(Ph₃P)₂] · 1/2CH₂Cl₂ crystallizes in the triclinic space group P1 : a = 1 103.1(4); b = 1 227.9(4); c = 1 711.3(5) pm; α = 70.48(3)°; β = 72.71(3)°; γ = 80.03(3)°; Z = 2. The rhenium atom exhibits a distorted octahedral coordination with the Cl atoms and the phosphine ligands in trans positions. As a consequence of the competition of the nitrene ligand and the trans-coordinated methoxy group the Re?;N bond length is slightly lengthened to 173.2(7) pm, while the Re? O bond length of 193.4(6) pm is short. The bond angles Re? N? C70 and Re? O? C80 are 173.3(7)° and 139.1(7)°, respectively.     

Synthese und Struktur der Komplexe [(n‐Bu)4N]2[{(THF)Cl4Re≡N}2PdCl2], [Ph4P]2[(THF)Cl4Re≡N‐PdCl(μ‐Cl)]2 und [(n‐Bu)4N]2[Pd3Cl8]

Synthesis and Crystal Structure of the Complexes [(n‐Bu)₄N]₂[{(THF)Cl₄Re≡N}₂PdCl₂], [Ph₄P]₂[(THF)Cl₄Re≡N‐PdCl(μ‐Cl)]₂ and [(n‐Bu)₄N]₂[Pd₃Cl₈] The threenuclear complex [(n‐Bu)₄N]₂[{(THF)Cl₄Re≡N}₂ PdCl₂] ( 1 ) is obtained in THF by the reaction of PdCl₂(NCC₆H₅)₂ with [(n‐Bu)₄N][ReNCl₄] in the molar ration 1:2. It forms orange crystals with the composition 1· THF crystallizing in the monoclinic space group C2/c with a = 2973.3(2); b = 1486.63(7); c = 1662.67(8)pm; β = 120.036(5)° and Z = 4. If the reaction is carried out with PdCl₂ instead of PdCl₂(NCC₆H₅)₂, orange crystals of hitherto unknown [(n‐Bu)₄N]₂[Pd₃Cl₈] ( 3 ) are obtained besides some crystals of 1· THF. 3 crystallizes with the space group P1¯ and a = 1141.50(8), b = 1401.2(1), c = 1665.9(1)pm, α = 67.529(8)°, β = 81.960(9)°, γ = 66.813(8)° and Z = 2. In the centrosymmetric complex anion [{(THF)Cl₄Re≡N}₂PdCl₂]^2— a linear PdCl₂ moiety is connected in trans arrangement with two complex fragments [(THF)Cl₄Re≡N]^— via asymmetric nitrido bridges Re≡N‐Pd. For Pd(II) thereby results a square‐planar coordination PdCl₂N₂. The linear nitrido bridges are characterized by distances Re‐N = 163.8(7)pm and Pd‐N = 194.1(7)pm. The crystal structure of 3 contains two symmetry independent, planar complexes [Pd₃Cl₈]^2— with the symmetry 1¯, in which the Pd atoms are connected by slightly asymmetric chloro bridges. By the reaction of equimolar amounts of [Ph₄P][ReNCl₄] and PdCl₂(NCC₆H₅)₂ in THF brown crystals of the heterometallic complex, [Ph₄P]₂[(THF)Cl₄Re≡N‐PdCl(μ‐Cl)]₂ ( 2 ) result. 2 crystallizes in the monoclinic space group P2₁/n with a = 979.55(9); b = 2221.5(1); c = 1523.1(2)pm; β = 100.33(1)° and Z = 2. In the central unit ClPd(μ‐Cl)₂PdCl of the centrosymmetric anionic complex [(THF)Cl₄Re≡N‐PdCl(μ‐Cl)]₂^2— the coordination of the Pd atoms is completed by two nitrido bridges Re≡N‐Pd to nitrido complex fragments [(THF)Cl₄Re≡N]^— forming a square‐planar arrangement for Pd(II). The distances in the linear nitrido bridges are Re‐N = 163.8(9)pm and Pd‐N = 191.5(9)pm.     

Synthese und Kristallstruktur von [(Me3Si)2BiCu(PMe3)3], dem ersten Komplex mit einer Bismut—Kupfer‐Bindung

Synthesis and Crystal Structure of [(Me₃Si)₂BiCu(PMe₃)₃] — the First Complex with a Bismuth—Copper Bond The reaction of CuO^t Bu with PMe₃ and Bi(SiMe₃)₃ in hexane yields the phosphine‐stabilized complex [(Me₃Si)₂Bi‐Cu( PMe₃)₃]. This synthesis gave rise to the first binuclear Bi—Cu compound to be structurally characterized by X‐ray crystallography.     

Synthese,Struktur und magnetische Eigenschaften der Verbindungen NaMIIZr2F11 (MII = Ti,V und Cu) und einem Anhang über NaPdZr2F11

Synthesis, Structure, and Magnetic Properties of Compounds NaM^IIZr₂F₁₁ (M^II = Ti, V, Cu) and a Notice on NaPdZr₂F₁₁ By synthesizing NaTiZr₂F₁₁ in form of red single crystals, it was possible to obtain a complex fluoride with Ti²⁺ for the first time. It crystallizes like the analogous greenish blue vanadium compound isotypic to AgPdZr₂F₁₁ [1] monoclinic, spacegroup C2/m–C (No. 12) with a = 918.0/911.5 pm, b = 682.6/675.7 pm, c = 780.8/776.6 pm, β = 116.2/116.2º and Z = 2. Colourless NaCuZr₂F₁₁ however crystallizes as a result of the Jahn-Teller distortion of Cu²⁺ triclinic (space group P1 –C (No. 2), a = 552.7 pm, b = 568.2 pm, c = 768.0 pm, α = 111.0º, β = 97.4º, γ = 106.4º) and is – as expected – isotypic to NaAgZr₂F₁₁ [1].     

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.     

Synthese und Kristallstrukturen von Chlororhenaten(III) mit den zweiwertigen Kationen Ethylendiammonium und Piperazinium:(EnH2)2(Pipzh2)[Re3Cl12]2· 6H2O,und (PipzH2) [Re3Cl12]CI·H2O und (Pipzh2) [Re3Cl11(H2O)]·3H2O

Synthesis and Crystal Structures of Chlororhenates(III) with the Divalent Cations Ethylenediammonium and Piperazinium: (EnH₂)₂(PipzH₂) [Re₃Cl₁₂]₂·6H₂O, (EnH₂) (PipzH₂) [Re₃Cl₁₂]Cl· H₂O, and (PipzH₂) [Re₃Cl₁₁(H₂O)] · 3H₂O The deep red salt (EnH₂)₂(PipzH₂)[Re₃CI₁₂] · 6 H₂O ( 1 ), (EnH₂)(PipzH₂)[Re₃Cl₁₂]CI · H₂O ( 2 ), and (PipzH₂)[Re₃Cl₁₁(H₂O)] · 3H₂O ( 3 ) crystallize upon evaporation from hydrochloride acid solutions of ReCl₃ on addition of ethylenediammonium chloride (EnH₂Cl₂) and/or piperazinium chloride (PipzH₂Cl₂). The crystal structures have been determined from four-circle diffractometer data. 1: monoclinic; a = 1889.63(11), b = 1615.82(8), c = 790.28(4)pm; β = 101.354(5)°; Z = 2; P2₁/n; R = 0.119, R_w = 0.070. 2: triclinic; a = 1330.35(4), b = 1051.14(5), c = 1165.32(6)pm; α = 122.308(4), β = 102.412(3), γ = 92.226(4)°; Z = 2, P1 ; R = 0.092, R_w = 0.059. 3: orthorhombic; a = 971.43(4), b = 1619.51(7), c = 1478.87(6)pm; Z = 4; Pbcm; R = 0.034, R_w = 0.032.