Reaktionen von tBu2P–P=P(Me)tBu2 mit (Et3P)2NiCl2 und [{η2‐C2H4}Ni(PEt3)2]

Coordination Chemistry of P‐rich Phosphanes and Silylphosphanes. XXIII. Reactions of ^tBu₂P–P=P(Me)^tBu₂ with (Et₃P)₂NiCl₂ and [{η²‐C₂H₄}Ni(PEt₃)₂] ^tBu₂P–P=P(Me)^tBu₂ ( 1 ) forms with (Et₃P)₂NiCl₂ ( 2 ) and Na(Nph) the [μ‐(1,3 : 2,3‐η‐^tBu₂P₄^tBu₂){Ni(PEt₃)Cl}₂] ( 3 ) as main product. Using Na/Hg instead as reducing agent the Ni⁰ compounds [{η²‐^tBu₂P–P}Ni(PEt₃)₂] ( 4 ), [{η²‐^tBu₂P–P=P–P^tBu₂}Ni(PEt₃)₂] ( 5 ) and [(Et₃P)Ni(μ‐P^tBu₂)]₂ ( 6 ) with four‐membered Ni₂P₂ ring result. [{η²‐C₂H₄}Ni(PEt₃)₂] yields with 1 also 4 . The compounds were characterized by ¹H and ³¹P{¹H} NMR investigations and 3 also by a single crystal X‐ray analysis. It crystallizes triclinic in the space group P 1 with a = 1129.4(2), b = 1256.8(3), c = 1569.5(3) pm, α = 72.44(3)°, β = 70.52(3)° and γ = 74.20(3)°.     

Zur Umsetzung von Kupfer(I)‐ und Kupfer(II)‐Salzen mit P(C6H4CH2NMe2‐2)3 ‐ die Festkörperstrukturen von {[P(C6H4CH2NMe2‐2)3]CuOClO3}ClO4, {[P(C6H4CH2NMe2‐2)3]Cu}ClO4, [P(C6H4CH2NMe2‐2)3]CuONO2 und [P(C6H4CH2NMe2‐2)2(C6H4CH2NMe2H+NO3‐‐2)]CuONO2

Reaction Behaviour of Copper(I) and Copper(II) Salts Towards P(C₆H₄CH₂NMe₂‐2)₃ ‐ the Solid‐State Structures of {[P(C₆H₄CH₂NMe₂‐2)₃]CuOClO₃}ClO₄, {[P(C₆H₄CH₂NMe₂‐2)₃]Cu}ClO₄, [P(C₆H₄CH₂NMe₂‐2)₃]CuONO₂ and [P(C₆H₄CH₂NMe₂‐2)₂(C₆H₄CH₂NMe₂H⁺NO₃^‐‐2)]CuONO₂ The reaction behaviour of P(C₆H₄CH₂NMe₂‐2)₃ ( 1 ) towards different copper(II) and copper(I) salts of the type CuX₂ ( 2a : X = BF₄, 2b : X = PF₆, 2c : X = ClO₄, 2d : X = NO₃, 2e : X = Cl, 2f : X = Br, 13 : X = O₂CMe) and CuX ( 5a : X = ClO₄, 5b : X = NO₃, 5c : X = Cl, 5d : X = Br) is discussed. Depending on X, the transition metal complexes [P(C₆H₄CH₂NMe₂‐2)₃Cu]X₂ ( 3a : X = BF₄, 3b : X = PF₆), {[P(C₆H₄CH₂NMe₂‐2)₃]CuX}X ( 4 : X = ClO₄, 11a : X = Cl, 11b : X = Br, 14 : X = O₂CMe), {[P(C₆H₄CH₂NMe₂‐2)₃]Cu}ClO₄ ( 6 ), [P(C₆H₄CH₂NMe₂‐2)₃]CuX ( 7a : X = Cl, 7b : X = Br, 10 : X = ONO₂), [P(C₆H₄CH₂NMe₂‐2)₂(C₆H₄CH₂NMe₂H⁺NO₃^‐‐2)]CuONO₂ ( 9 ) and [P(C₆H₄CH₂NMe₂‐2)₃]CuCl}CuCl₂ ( 12 ) are accessible. While in 3a , 3b and 6 the phosphane 1 preferentially acts as tetrapodale ligand, in all other species only the phosphorus atom and two of the three C₆H₄CH₂NMe₂ side‐arms are datively‐bound to the appropriate copper ion. In solution a dynamic behaviour of the latter species is observed. Due to the coordination ability of X in 3a , 3b and 6 non‐coordinating anions X^‐ are present. However, in 4 one of the two perchlorate ions forms a dative oxygen‐copper bond and the second perchlorate ion acts as counter ion to {[P(C₆H₄CH₂NMe₂‐2)₃]CuOClO₃}⁺. In 7 , 9 and 10 the fragments X (X = Cl, Br, ONO₂) form a σ‐bond with the copper(I) ion. The acetate moiety in 14 acts as chelating ligand as it could be shown by IR‐spectroscopic studies. All newly synthesised cationic and neutral copper(I) and copper(II) complexes are representing stable species. Redox processes are involved in the formation of 9 and 12 by reacting 1 with 2 . The solid‐state structures of 4 , 6 , 9 and 10 are reported. In the latter complexes the copper(II) ( 4 ) or copper(I) ion ( 6 , 9 , 10 ) possesses the coordination number 4. This is achieved by the formation of a phosphorus‐ and two nitrogen‐copper‐ ( 4 , 9 , 10 ) or three ( 6 ) nitrogen‐copper dative bonds and a coordinating ( 4 ) or σ‐binding ( 9 , 10 ) ligand X. In 6 all three nitrogen and the phosphorus atoms are coordinatively bound to copper, while X acts as non‐coordinating counter‐ion. Based on this, the respective copper ion occupies a distorted tetrahedral coordination sphere. While in 4 and 10 a free, neutral Me₂NCH₂ side‐arm is present, which rapidly exchanges in solution with the coordinatively‐bound Me₂NCH₂ fragments, this unit is protonated in 10 . NO₃^‐ acts as counter ion to the CH₂NMe₂H⁺ moiety. In all structural characterized complexes 6‐membered boat‐like CuPNC₃ cycles are present.     

Zum Einfluß der PR3‐Liganden auf Bildung und Eigenschaften der Phosphinophosphiniden‐Komplexe [{η2‐tBu2P–P}Pt(PR3)2] und [{η2‐tBu2P1–P2}Pt(P3R3)(P4R′3)]

Coordination Chemistry of P‐rich Phosphanes and Silylphosphanes XXI The Influence of the PR₃ Ligands on Formation and Properties of the Phosphinophosphinidene Complexes [{η²‐^tBu₂P–P}Pt(PR₃)₂] and [{η²‐^tBu₂P¹–P²}Pt(P³R₃)(P⁴R′₃)] (R₃P)₂PtCl₂ and C₂H₄ yield the compounds [{η²‐C₂H₄}Pt(PR₃)₂] (PR₃ = PMe₃, PEt₃, PPhEt₂, PPh₂Et, PPh₂Me, PPh₂ⁱPr, PPh₂^tBu and P(p‐Tol)₃); which react with ^tBu₂P–P=PMe^tBu₂ to give the phosphinophosphinidene complexes [{η²‐^tBu₂P–P}Pt(PMe₃)₂], [{η²‐^tBu₂P–P}Pt(PEt₃)₂], [{η²‐^tBu₂P–P}Pt(PPhEt₂)₂], [{η²‐^tBu₂P–P}Pt(PPh₂Et)₂], [{η²‐^tBu₂P–P}Pt(PPh₂Me)₂], [{η²‐^tBu₂P–P}Pt(PPh₂ⁱPr], [{η²‐^tBu₂P–P}Pt(PPh₂^tBu)₂] and [{η²‐^tBu₂P–P}Pt(P(p‐Tol)₃)₂]. [{η²‐^tBu₂P–P}Pt(PPh₃)₂] reacts with PMe₃ and PEt₃ as well as with ^tBu₂PMe, PⁱPr₃ and P(c‐Hex)₃ by substituting one PPh₃ ligand to give [{η²‐^tBu₂P¹–P²}Pt(P³Me₃)(P⁴Ph₃)], [{η²‐^tBu₂P¹–P²}Pt(P³Ph₃)(P⁴Me₃)], [{η²‐^tBu₂P¹–P²}Pt(P³Et₃)(P⁴Ph₃)], [{η²‐^tBu₂P¹–P²}Pt(P³Me^tBu₂)(P⁴Ph₃)], [{η²‐^tBu₂P¹–P²}Pt(P³ⁱPr₃)(P⁴Ph₃)] and [{η²‐^tBu₂P¹–P²}Pt(P³(c‐Hex)₃)(P⁴Ph₃)]. With ^tBu₂PMe, [{η²‐^tBu₂P–P}Pt(P(p‐Tol)₃)₂] forms [{η²‐^tBu₂P¹–P²}Pt(P³Me^tBu₂)(P⁴(p‐Tol)₃)]. The NMR data of the compounds are given and discussed with respect to the influence of the PR₃ ligands.     

Kristallstrukturen der iso‐Thiocyanatoberyllate (Ph4P)2[Be(NCS)4] und (Ph4P)4[{Be2(NCS)4(μ‐NCS)2}{Be2(NCS)6(μ‐H2N2C2S2)}]

Bis(tetraphenylphosphonium) hexachloridodiberyllate, (Ph₄P)₂[Be₂Cl₆], reacts with excess trimethylsilyl‐iso‐thiocyanate to give a mixture of colourless single crystals of (Ph₄P)₂[Be(NCS)₄] ( 1 ) and (Ph₄P)₄[{Be₂(NCS)₄(μ‐NCS)₂}{Be₂(NCS)₆(μ‐H₂N₂C₂S₂)}] ( 2 ), which can be separated by selection. Both complexes were characterized by X‐ray diffraction. Compound 1 can be prepared without by‐products by treatment of (Ph₄P)₂[BeCl₄] with excess Me₃SiNCS in dichloromethane solution. 1 : Space group I4₁/a, Z = 4, lattice dimensions at 100(2) K: a = b = 1091.2(1), c = 3937.1(3) pm, R₁ = 0.0474. The [Be(NCS)₄]^2– ion of 1 forms tetragonally distorted tetrahedral anions with Be–N distances of 168.4(2) pm and weak intermolecular S ··· S contacts along [100] and [010]. 2 ·4CH₂Cl₂: Space group P , Z = 1, lattice dimensions at 100(2) K: a = 919.5(1), b = 1248.3(1), c = 2707.0(2) pm, α = 101.61(1) °, β = 95.08(1) °, γ = 94.52(1) °, R₁ = 0.103. Compound 2 contains two different anionic complexes in the ratio 1:1. In {Be₂(NCS)₄(μ‐NCS)₂}^2–, the beryllium atoms are connected by (NCS)^– bridging groups forming centrosymmetric eight‐membered Be₂(NCS)₂ rings with distances Be–N of 168(1) pm and Be–S of 235.2(9) pm. The second anion {Be₂(NCS)₆(μ‐H₂N₂C₂S₂)}^2– consists of two {Be(NCS)₃}^– units, which are linked by the nitrogen atoms of the unique dimeric cyclo‐addition product of HNCS with Be–N distances of 179(1) pm.     

Bildung und Struktur des [{cyclo‐P4(PtBu2)4}{Ni(CO)2}2]

Coordination Chemistry of P‐rich Phosphanes and Silylphosphanes. XXVI. Formation and Structure of [{ cyclo ‐P₄(P^tBu₂)₄}{Ni(CO)₂}₂] [{cyclo‐P₄(P^tBu₂)₄}{Ni(CO)₂}₂] is formed by reaction of the cyclotetraphosphane P₄(P^tBu₂)₄ with [Ni(CO)₄]. Each Ni(CO)₂ unit is coordinated by two adjacent ^tBu₂P groups forming two five‐membered P₄Ni rings above and below the planar cyclotetraphosphane ring, respectively. The compound crystallizes in the triclinic space group P 1 (No. 2) with a = 893.29(5), b = 1140.75(7), c = 1235.52(8) pm, α = 109.179(7), β = 100.066(7), γ = 97.595(7)° and Z = 1.     

Two (E)‐2‐({[4‐(dialkylamino)phenyl]imino}methyl)‐4‐nitrophenols

The slow evaporation of analytical NMR samples resulted in the formation of crystals of (E)‐2‐({[4‐(dimethylamino)phenyl]imino}methyl)‐4‐nitrophenol, C₁₅H₁₅N₃O₃, (I), and (E)‐2‐({[4‐(diethylamino)phenyl]imino}methyl)‐4‐nitrophenol, C₁₇H₁₉N₃O₃, (II). Despite the small structural difference between these two N‐salicylideneaniline derivatives, they show different space groups and diverse molecular packing. The molecules of both compounds are close to being planar due to an intramolecular O—H...N hydrogen bond. The 4‐alkylamino‐substituted benzene ring is inclined at an angle of 13.44 (19)° in (I) and 2.57 (8)° in (II) with respect to the 4‐nitro‐substituted phenol ring. Only very weak intermolecular π–π stacking and C—H...O interactions were found in these structures.     

Synthese,NMR‐Spektren und Molekülstruktur von [(CH3)2Ga{μ‐P(H)Si(CH3)3}2Ga(CH3)2{μ‐P(Si(CH3)3)2}Ga(CH3)2]

Synthesis, NMR Spectra and Structure of [(CH₃)₂Ga{μ‐P(H)Si(CH₃)₃}₂Ga(CH₃)₂{μ‐P(Si(CH₃)₃)₂}Ga(CH₃)₂] The title compound has been prepared in good yield by the reaction of [Me₂GaOMe]₃ (Me = CH₃) with HP(SiMe₃)₂ in toluene (ratio 1 : 1,1) and purified by crystallization from pentane or toluene, respectively. This organogallium compound forms (Ga–P)₃ ring skeletons with one Ga–P(SiMe₃)₂–Ga and two Ga–P(H)SiMe₃–Ga bridges and crystallizes in the monoclinic space group C2/c. The known homologous Al‐compound is isotypic, both (M^III–P)₃ heterocycles have twist‐conformations, the ligands of the monophosphane bridges have trans arrangements.     

[Co4P2(PtBu2)2(CO)8] und [{Co(CO)3}2P4tBu4] aus Co2(CO)8 und tBu2P–P=P(Me)tBu2

Coordination Chemistry of P‐rich Phosphanes and Silylphosphanes. XIX. [Co₄P₂(P^tBu₂)₂(CO)₈] and [{Co(CO)₃}₂P₄^tBu₄] from Co₂(CO)₈ and ^tBu₂P–P=P(Me)^tBu₂ Co₂(CO)₈ reacts with ^tBu₂P–P=P(Me)^tBu₂ yielding the compounds [Co₄P₂(P^tBu₂)₂(CO)₈] ( 1 ) and [{η^2tBu₂P=P–P=P^tBu₂}{Co(CO)₃}₂] ( 2 a ) cis, ( 2 b ) trans. In 1 , four Co and two P atoms form a tetragonal bipyramid, in which two adjacent Co atoms are μ₂‐bridged by ^tBu₂P groups. Additionally, two CO groups are linked to each Co atom. In 2 a and 2 b , each of the Co(CO)₃ units is η²‐coordinated to the terminal P₂ units resulting in the cis‐ and trans‐configurations 2 a and 2 b . 1 crystallizes in the orthorhombic space group Pnnm (No. 58) with a = 879,41(5), b = 1199,11(8), c = 1773,65(11) pm. 2 a crystallizes in the monoclinic space group P2₁/n (No. 14) with a = 875,97(5), b = 1625,36(11), c = 2117,86(12) pm, β = 91,714(7)°. 2 b crystallizes in the triclinic space group P 1 (No. 2) with a = 812,00(10), b = 843,40(10), c = 1179,3(2) pm, α = 100,92(2)°, β = 102,31(2)°, γ = 102,25(2)°.     

2‐{[(4‐Methylphenyl)sulfonyl]amino}phenyl 4‐methylbenzenesulfonate

The title compound, C₂₀H₁₉NO₅S₂, crystallizes as an almost 2:1 mixture of two molecular orientations (described as Orient‐A and Orient‐B). The consequences of these two orientations is the formation of three types of N—H...O hydrogen‐bonded dimers in which the (Orient‐A + Orient‐A) dimers are likely to be the most stable, while the mixed (Orient‐A + Orient‐B) dimers are more frequent. Extra interactions in the form of C—H...O and C—H...π interactions act to further stabilize these dimers and probably allow the less energetically favourable (Orient‐A + Orient‐B) and (Orient‐B + Orient‐B) hydrogen‐bonded dimers to exist by preventing their conversion to (Orient‐A + Orient‐A)‐only hydrogen‐bonded dimers during the crystal‐growth process.     

Synthesis and Crystal Structures of the Novel Tetrameric Nitrido Complexes [{cyclo-ReN}4(S2CNEt2)6(MeOH)2(PPh3)2][BPh4]2 · CH2Cl2 · 2 H2O and [{cyclo-ReN}4(S2CNEt2)4Cl4(PMe2Ph)4] · 2 acetone

Novel tetrameric rhenium(V) complexes have been prepared from [ReNCl₂(PPh₃)₂] and [ReN(PMe₂Ph)(S₂CNEt)₂], respectively. [ReNCl₂(PPh₃)₂] reacts with 1.5 equivalents of KS₂CNEt₂ in methanol to yield the unusual dark red species [{cyclo-ReN}₄(S₂CNEt₂)₆(MeOH)₂(PPh₃)₂][BPh₄]₂ · CH₂Cl₂ · 2 H₂O ( 1 ). The crystal structure of the tetramer (triclinic, space group P1, a = 13.842(2), b = 15.213(2), c = 16.796(3) Å, α = 67.88(1), β = 70.90(1), γ = 88.05(1)°, U = 3080.2(8) ų, Z = 1) shows four rhenium atoms in a square configuration which are bridged via linear asymmetric Re≡N–Re groups with bond lengths of about 169 and 203 pm. The molecule contains a centre of symmetry with two distinct octahedral rhenium environments. The first rhenium environment contains two bidentate dithiocarbamate ligands which complete the octahedral geometry and the second contains a bidentate dithiocarbamate ligand, coordinated methanol and has retained a single phosphine coligand. A symmetric compound containing the {cyclo-ReN}₄ core is obtained from the reaction of [ReN(PMe₂Ph)(S₂CNEt₂)₂] with Al₂Cl₆ in acetone. [{cyclo-ReN}₄(S₂CNEt₂)₄Cl₄(PMe₂Ph)₄] · 2 acetone ( 2 ) forms red crystals (monoclinic, space group C2/c, a = 21.432(6), b = 13.700(3), c = 28.060(9) Å, β = 102.37(1)°, U = 8048(4) Å3, Z = 4) with each rhenium atom coordinated by a bidentate dithiocarbamato, a phosphine and a chloro ligand. The non-planar 8-membered {ReN}₄ ring contains asymmetric Re≡N–Re bridges (mean values: 1.69 Å and 2.029 Å, respectively). In contrast, reaction of [ReNCl(S₂CNEt₂)(PMe₂Ph)₂] with one equivalent of K[S₂CN(Me)CH₂CH₂NMe₃]I gave the mixed dithiocarbamato-cation [ReN(S₂CNEt₂)(S₂CN(Me)CH₂CH₂NMe₃)(PMe₂Ph)]⁺ ( 3 ) which was isolated as a tetraphenylborate salt.     

Azidokomplexe von Vanadium(IV) und Vanadium(V): (Ph4P)2[VOCl2(μ‐N3)]2 und (Ph4P)2[VOCl(μ‐N3)(N3)2]2

Azido Complexes of Vanadium(IV) and Vanadium(V): (Ph₄P)₂[VOCl₂(μ‐N₃)]₂ and (Ph₄P)₂[VOCl(μ‐N₃)(N₃)₂]₂ (Ph₄P)₂[VOCl₂(μ‐N₃)]₂ ( 1 ) was prepared by reaction of (Ph₄P)[VO₂Cl₂] with trimethylsilylazide in the molar ratio 1:2 in dichloromethane solution to give dark green, moisture sensitive, non‐explosive single crystals. The reaction is accompanied by the formation of the dark blue side‐product (Ph₄P)₂[VOCl(μ‐N₃)(N₃)₂]₂ ( 2a ), which can be obtained as the main product by application of a large excess of Me₃SiN₃. Dark blue needles of 2a crystallize spontaneously from the CH₂Cl₂ solution within one hour at 4 °C. After standing at 4 °C under its mother liquid within 24 hours a first‐order phase transition of 2a occurs forming dark blue prismatic single crystals of 2b . According to single crystal X‐ray structure determinations, 2a and 2b crystallize in the same type of space group , however, with different lattice dimensions. The vanadium(IV) complex 1 is characterized by X‐ray structure determination and by vibrational spectroscopy (IR, Raman) as well as by EPR spectroscopy, whereas 2b is characterized by IR spectroscopy. 1 : Space group P2₁/n, Z = 2, a = 1009.5(1), b = 1226.6(2), c = 1943.0(2) pm, β = 98.42(1)°, R₁ = 0.0672. The complex anion forms centrosymmetric units with V₂N₂‐four‐membered rings with a V···V distance of 335.6(1) pm and coordination number five on the vanadium(IV) atoms. 2a : Space group , Z = 1, a = 1089.0(2), b = 1097.1(2), c = 1310.1(2) pm, α = 92.99(1)°, β = 106.12(2)°, γ = 117.05(2)°, V = 1309.8(4) ų, d_calc. = 1.440 g·cm^?3, R₁ = 0.0384. The complex anion forms centrosymmetric units of symmetry C_i with V₂N₂ four‐membered rings and VN bond lengths of 200.4(3) and 234.4(2) pm, respectively. The non‐bonding V···V distance amounts to 356.2(1) pm. 2b : Space group , Z = 1, a = 1037.3(2), b = 1157.6(2), c = 1177.2(2) pm, α = 98.48(2)°, ° = 103.82(2)°, γ = 106.33(2)°, V = 1281.8(4) ų, d_calc. = 1.471 g·cm^?3, R₁ = 0.0724. The structure of the complex anion is similar to the anion of 2a with VN bond lengths of the four‐membered V₂N₂ ring of 203.3(4) and 235.2(4) pm, respectively, and a non‐bonding V···V distance of 357.5(1) pm.     

Komplexchemie P‐reicher Phosphane und Silylphosphane. XXII. Die Bildung von [η2‐{tBu–P=P–SiMe3}Pt(PR3)2]aus (Me3Si)tBuP–P=P(Me)tBu2 und [η2‐{C2H4}Pt(PR3)2]

Coordination Chemistry of P‐rich Phosphanes and Silylphosphanes. XXII. The Formation of [η²‐{^tBu–P=P–SiMe₃}Pt(PR₃)₂] from (Me₃Si)^tBuP–P=P(Me)^tBu₂ and [η²‐{C₂H₄}Pt(PR₃)₂] (Me₃Si)^tBuP–P = P(Me)^tBu₂ reacts with [η²‐{C₂H₄}Pt(PR₃)₂] yielding [η²‐{^tBu–P=P–SiMe₃}Pt(PR₃)₂]. However, there is no indication for an isomer which would be the analogue to the well known [η²‐{^tBu₂P–P}Pt(PPh₃)₂]. The syntheses and NMR data of [η²‐{^tBu–P=P–SiMe₃}Pt(PPh₃)₂] and [η²‐{^tBu–P=P–SiMe₃}Pt(PMe₃)₂] as well as the results of the single crystal structure determination of [η²‐{^tBu–P=P–SiMe₃}Pt(PPh₃)₂] are reported.     

Die Kristallstruktur von (Ph4P)2[Be4Cl4(μ‐N3)6]

Suitable single crystals for X‐ray analysis of the recently published azido beryllate (Ph₄P)₂[Be₄Cl₄(μ‐N₃)₆] ( 1 ) [1] were obtained by a modified synthetic route, and the crystal structure of 1 was determined. The compound crystallizes isotypically with the corresponding bromo derivative [1] in the space group C2/c with 12 formula units per unit cell. Lattice dimensions at 193 K: a = 4125.5(1), b = 2001.7(1), c = 2050.4(1) pm, β = 101.05 (1)°, R₁ = 0.0359. The structure contains adamantanlike dianions [Be₄Cl₄(μ‐N₃)₆]^2? with a Be₄N₆ core forming by the bridging function of the α‐nitrogen atoms of the azido groups.