首页 | 本学科首页   官方微博 | 高级检索  
相似文献
 共查询到20条相似文献,搜索用时 31 毫秒
1.
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 .  相似文献   

2.
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.  相似文献   

3.
Synthesis and Structure of Two- and Threenuclear Heterometallic Complexes with Nitrido Bridges between Re and Mo The reaction of ReNCl2(PMe2Ph)3 with MoCl4(NCEt)2 yields the heterometallic threenuclear complex [{(Me2PhP)3(EtCN)ClRe≡N–}2MoCl4][MoNCl5]. The anion [MoNCl5]2– presumably results from a transfer of the nitrido ligand from the Re to the Mo atom. The air-sensitive compound is paramagnetic with μeff = 2.87 B. M. at room temperature. A reduction of the magnetic moment to 1.74 B.M at 20 K starts at 140 K. The complex crystallizes in the orthorhombic space group Pca21 with a = 2430(1), b = 1328(1), c = 2436.3(2) pm, Z = 4. With bond angles Re–N–Mo of 164° and 167° the nitrido bridges are almost linear. The distances Re–N of 169 and 170 pm can be interpreted with triple bonds. The Mo–N bond lengths of 210 and 211 pm correspond to single bonds. In the anion [MoNCl5]2– the distance Mo≡N is 167 pm. Hydrolysis of the threenuclear complex results in a cleavage of one of the nitrido bridges to yield (Me2PhP)3(EtCN)ClRe≡N–MoOCl4. The compound is paramagnetic with μeff = 1.71 B.M. at room temperature. It crystallizes in the orthorhombic space group Pbca with a = 1718.5(4), b = 2037(1), c = 2041.1(7) pm, Z = 8. In the dinuclear complex the [MoOCl4] unit is only weakly coordinated to the nitrido ligand with Mo–N = 246.5 pm, while the distance of the Re≡N bond of 168.1 pm is almost unchanged in comparison with a terminal bond. The bond angle Re≡N–Mo is 165.6°.  相似文献   

4.
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 Ci 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.  相似文献   

5.
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.  相似文献   

6.
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.  相似文献   

7.
Synthesis and Structure of (Me2PhP)3Cl2Re≡N–ReCl4(PMe2Ph), a Mixed Valent Dinuclear Complex with a Nitrido Bridge between ReV and ReIV 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 μeff = 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)°.  相似文献   

8.
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.  相似文献   

9.
Synthesis and Structures of the Multinuclear Rhenium Nitrido Complexes [Re2N2Cl4(PMe2Ph)4(MeCN)] and [Re4N3Cl9(PMe2Ph)6] The binuclear rhenium complex [Re2N2Cl4(PMe2Ph)4(MeCN)] ( 1 ) is obtained as a byproduct of the synthesis of [(Me2PhP)3(MeCN)ClReNZrCl5] from [ReNCl2(PMe2Ph)3] and [ZrCl4(MeCN)2] in toluene. It crystallizes as 1 · 2 toluene in the monoclinic space group P21/n with a = 1517.0(3); b = 1847.7(2); c = 1952.4(6) pm; β = 106.44(1)° and Z = 4. The two Re atoms are connected by an asymmetric nitrido bridge Re≡N–Re with distances Re–N of 169.9(5) and 208.7(5) pm. In course of the reaction of [ReNCl2(PMe2Ph)3] with [ZrCl4(THF)2] in CH2Cl2 hydrochloric acid is formed by acting of the Lewis acid on the solvent. HCl protonates and eliminates phosphine ligands of the educt [ReNCl2(PMe2Ph)3] to form the phosphonium salt [PMe2PhH]2[ZrCl6] ( 2 ). It crystallizes in the monoclinic space group C2/c with a = 1536.9(3); b = 1148.8(1); c = 1402.2(3) pm, β = 100.70(2)° and Z = 4. The remaining fragments of the rhenium complex combine to yield the tetranuclear mixed valent complex [Re4N3Cl9(PMe2Ph)6] ( 3 ), crystallizing as 3 · CH2Cl2 in the triclinic space group P 1 with a = 1312.9(19); b = 1661.4(2); 1897.1(2) pm; α = 78.62(1)°; β = 86.77(1)°; γ = 68.28(1)° and Z = 2. The four Re atoms occupy the corners of a tetrahedron. Its edges are formed by three nitrido and three chloro bridges. The asymmetric nitrido bridges Re≡N–Re are characterized by short distances in the range of 172(2) to 176(3) pm and long distances of 194(3) to 204(2) pm. The angles Re–N–Re are between 154(1) and 160(1)°.  相似文献   

10.
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.  相似文献   

11.
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.  相似文献   

12.
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.  相似文献   

13.
New Trinuclear Rhenium Complexes with Bridging Nitrido Ligands Trinuclear complexes with bridging nitrido ligands between the rhenium atoms are formed when [ReN(Et2dtc)2 · (Me2PhP)] (Et2dtc = N,N‐diethyldithiocarbamate) reacts with TlCl or Pr(O3SCF3)3. [Cl(Me2PhP)2(Et2dtc)Re≡N–Re(N) · Cl2(Me2PhP)–N≡Re(Et2dtc)(Me2PhP)2Cl] and [(Et2dtc)2 · (Me2PhP)Re≡N–Re(N)(Et2dtc)(Me2PhP)–N≡Re(Me2PhP) · (Et2dtc)2]+ contain two almost linear, asymmetric nitrido bridges. Additional, terminal nitrido ligands are located at the middle rhenium atoms.  相似文献   

14.
Synthesis, Structure, and Photolysis of Isocyanato Complexes of Rhenium The ReIII isocyanato complex Re(NCO)3(PMe2Ph)3 yields from the reaction of ReCl3(PMe2Ph)3 with an excess of NaOCN in EtOH. It crystallizes in the triclinic space group P 1 with a = 991.8(6), b = 1180.7(6), c = 1348.8(5) pm, α = 89.85(1)°, β = 94.12(1), γ = 111.56(1)°, Z = 2. In the mononuclear complex with an octahedral coordination of the Re atoms the phosphine and isocyanato ligands exhibit a meridional arrangement. By using a deficient amount of NaOCN the mono isocyanato complex Re(NCO)Cl2(PMe2Ph)3 is formed, and part of the educt is transformed to its isomer [(Me2PhP)3Re(μ-Cl)3Re(PMe2Ph)3]Cl3. The mono isocyanato complex forms monoclinic crystals with the space group P21/n and a = 1467.5(7), b = 1310.6(7), c = 1603.2(8) pm, β = 112.08(1)°, Z = 4. The isocyanato ligand is in trans position to a Cl atom, and the phosphine ligands are coordinated in a meridional arrangement. [(Me2PhP)3Re(μ-Cl)3Re(PMe2Ph)3]Cl3 · 2 EtOH crystallizes in the hexagonal space group P63/m with a = 1332.6(2), c = 2300.1(7) pm, Z = 2. The dinuclear complex cation occupies with its center a special position with the symmetry C3h. Photolysis of Re(NCO)Cl2(PMe2Ph)3 results in the cleavage of the isocyanato ligand with release of CO and formation of the nitrido complex ReNCl2(PMe2Ph)3. The reaction of ReNCl2(PMe2Ph)3 with NaOCN affords the complex ReN(NCO)2(PMe2Ph)3. It crystallizes in the space group P21/n with a = 943.0(3), b = 2635.2(4), c = 1212.6(5) pm, β = 109.88(1)°, Z = 4. In this nitrido complex, like in the educt, the phosphine ligands form a meridional arrangement. The nitrido ligand is in trans position to an isocyanato group. The distance Re≡N is 165.9(6) pm.  相似文献   

15.
[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.  相似文献   

16.
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 PtII 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 ReVI/PtII 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)]22— 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.  相似文献   

17.
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)]22— 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.  相似文献   

18.
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.  相似文献   

19.
Polysulfonylamines. CXVI. Destructive Complexation of the Dimeric Diorganyltin(IV) Hydroxide [Me2Sn(A)(μ‐OH)]2 (HA = Benzene‐1,2‐disulfonimide): Formation and Structures of the Mononuclear Complexes [Me2Sn(A)2(OPPh3)2] and [Me2Sn(phen)2]2⊕ · 2 A · MeCN Destructive complexation of the dimeric hydroxide [Me2Sn(A)(μ‐OH)]2, where A is deprotonated benzene‐1,2‐disulfonimide, with two equivalents of triphenylphosphine oxide or 1,10‐phenanthroline in hot MeCN produced, along with Me2SnO and water, the novel coordination compounds [Me2Sn(A)2(OPPh3)2] ( 3 , triclinic, space group P 1) and [Me2Sn(phen)2]2⊕ · 2 A · MeCN ( 4 , monoclinic, P21/c). In the uncharged all‐trans octahedral complex 3 , the heteroligands are unidentally O‐bonded to the tin atom, which resides on a crystallographic centre of inversion [Sn–O(S) 227.4(2), Sn–O(P) 219.6(2) pm, cis‐angles in the range 87–93°; anionic ligand partially disordered over two equally populated sites for N, two S and non‐coordinating O atoms]. The cation occurring in the crystal of 4 has a severely distorted cis‐octahedral C2N4 coordination geometry around tin and represents the first authenticated example of a dicationic tin(IV) dichelate [R2Sn(L–L′)2]2⊕ to adopt a cis‐structure [C–Sn–C 108.44(11)°]. The five‐membered chelate rings are nearly planar, with similar bite angles of the bidentate ligands, but unsymmetric Sn–N bond lengths, each of the longer bonds being trans to a methyl group [ring 1: N–Sn–N 71.24(7)°, Sn–N 226.81(19) and 237.5(2) pm; ring 2: 71.63(7)°, 228.0(2) and 232.20(19) pm]. In both structures, the bicyclic and effectively CS symmetric A ions have their five‐membered rings distorted into an envelope conformation, with N atoms displaced by 28–43 pm from the corresponding C6S2 mean plane.  相似文献   

20.
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 ).  相似文献   

设为首页 | 免责声明 | 关于勤云 | 加入收藏

Copyright©北京勤云科技发展有限公司  京ICP备09084417号