[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)°.     

Stannylierungsexperimente mit NH-funktionellen Aminoiminophosphoranen. Synthese und Struktur der tricyclischen Stannaphosphazene [Me2Sn(tBu2PN)NH]2 und [nBu2Sn(Ph2PN)2NH]2

Stannylation Experiments with NH-functional Aminoiminophosphoranes. Synthesis and Structure of the Tricyclic Stannaphosphazenes [Me₂Sn(^tBu₂PN)NH]₂ and [ⁿBu₂Sn(Ph₂PN)₂NH]₂ Aminoiminophosphoranes ^tBu₂P(NH)NH₂ ( 1 ) and (H₂NPPh₂)N(Ph₂PNH) ( 2 ) react with diaminostannanes R₂Sn(NEt₂)₂ by cyclocondensation to give cyclostannaphosphazenes [Me₂Sn(^tBu₂PN)NH]₂ ( 3 ) and [R₂Sn(Ph₂PN)₂NH]₂ ( 4 a , b ) ( a : R = Me, b : R = ⁿBu). With 2 and Me₃SnNEt₂ the ring compound Me₂Sn(Ph₂PN)₂NSnMe₃ ( 5 ) besides Me₄Sn is formed by per-N-stannylation and Sn-methyl group transfer. The crystal structures of 3 and 4 b were determined by X-ray structure analysis. 3 forms a planar heterotricyclus containing three four-membered rings with two pentacoordinated tin atoms (space group P 1 (No. 2); Z = 1). 4 b consists of a tricyclic molecule with two puckered six-membered rings and one planar four membered tin-nitrogen ring with two pentacoordinated tin atoms (space group P 1 (No. 2); Z = 1).     

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)°.     

Phosphinophosphiniden-Phosphorane tBu2P?P = P(R)tBu2 aus Li(THF)2[η2-(tBu2P)2P] und Alkylhalogeniden

The Phosphinophosphinidene-phosphoranes ^tBu₂P? P = P(R)^tBu₂ from Li(THF)₂[η²-(^tBu₂P)₂P] and Alkyl Halides We report the formation of ^tBu₂P? P = P(R)^tBu₂ a and (^tBu₂)₂PR b (with R = Me, Et, ⁿPr, ⁱPr, ⁿBu, PhCH₂, H₂C = CH? CH₂ and CF₃) reactions of Li(THF)₂[η²-(^tBu₂P)₂P] 2 with MeCl, MeI, EtCl, EtBr, ⁿPrCl, ⁿPrBr, ⁱPrCl, ⁿBuBr, PhCH₂Cl, H₂C = CH? CH₂Cl or CF₃Br. In THF solutions the ylidic compounds a predominate, whereas in pentane the corresponding triphosphanes b are preferrably formed. With ClCH₂? CH = CH₂ only b is produced; CF₃Br however yields both ^tBu₂P? P = P(Br)^tBu₂ and ^tBu₂P? P = P(CF₃)^tBu₂, but no b . The ratio of a:b is influenced by the reaction temperature, too. The compounds ^tBu₂P? P = P(Et)^tBu₂ 4a and (^tBu₂P)₂PEt 4 b , e. g., are produced in a ratio of 4:3 at ?70°C in THF, and 1:1 at 20°C; whereas 1:1 is obtained at ?70°C in pentane, and 1:2 at 20°C. Neither ^tBuCl nor H₂C = CHCl react with 2 . The compounds a decompose thermally or under UV irradiation forming ^tBu₂PR and the cyclophosphanes (^tBu₂P)_nP_n.     

Die Reaktion von tBu2P‐P=P(Me)tBu2 mit [Fe2(CO)9] und [(η2‐C8H14)2Fe(CO)3]

^tBu₂P‐P=P(Me)^tBu₂ reacts with [Fe₂(CO)₉] to give [μ‐(1, 2, 3:4‐η‐^tBu₂P¹‐P²‐P³‐P^4tBu₂){Fe(CO)₃}{Fe(CO)₄}] ( 1 ) and [trans‐(^tBu₂MeP)₂Fe(CO)₃]( 2 ). With [(η²‐C₈H₁₄)₂Fe(CO)₃] in addition to [μ‐(1, 2, 3:4‐η‐^tBu₂P¹‐P²‐P³‐P^4tBu₂){Fe(CO)₂PMe^tBu₂}‐{Fe(CO)₄}] ( 10 ) and 2 also [(μ‐P^tBu₂){μ‐P‐Fe(CO)₃‐PMe^tBu₂}‐{Fe(CO)₃}₂(Fe‐Fe)]( 9 ) is formed. 1 crystallizes in the monoclinic space group P2₁/c with a = 875.0(2), b = 1073.2(2), c = 3162.6(6) pm and β = 94.64(3)?. 2 crystallizes in the monoclinic space group P2₁/c with a = 1643.4(7), b = 1240.29(6), c = 2667.0(5) pm and β = 97.42(2)?. 9 crystallizes in the monoclinic space group P2₁/n with a = 1407.5(5), b = 1649.7(5), c = 1557.9(16) pm and β = 112.87(2)?.     

Offenkettige und cyclische As‐funktionalisierte Stannylarsine: Darstellung,Reaktionen und Struktur

Open‐Chain and Cyclic As‐functionalized Stannylarsines: Synthesis, Reactions, and Structure ^tBu₃SnAsH₂ ( 1 ) reacts with MeLi to form the lithium compound ^tBu₃SnAsHLi which reacts with ^tBu₂SnCl₂ to give the AsH‐functionalized bis(arsino)stannane ^tBu₂Sn(AsHSn^tBu₃)₂ ( 2 ). Metallation of diarsadistannetane (^tBu₂SnAsH)₂ ( 3 ) with two equivalents of ^tBuLi yields the dilithio compound (^tBu₂SnAsLi)₂ which reacts with Me₃SiCl or Me₃SnCl to give the corresponding As,As′‐bis‐substituted diarsadistannetanes (^tBu₂SnAsSiMe₃)₂ ( 4 ) and (^tBu₂SnAsSnMe₃)₂ ( 5 ), respectively. The novel compounds are characterized by NMR (¹H, ¹¹⁹Sn) and mass spectroscopy, ring compounds 4 and 5 further by X‐ray structure analysis. In the solid state both ring compounds contain molecules with planar tin‐arsenic rings and two trans‐configurated Me₃Si‐ or Me₃Sn‐ring substituents (space group P2₁/n (No. 14), Z = 2).     

Die Reaktionen von tBu2P–P=P(Me)tBu2 und (Me3Si)tBuP–P=P(Me)tBu2 mit PR3

The Reactions of ^tBu₂P–P=P(Me)^tBu₂ and (Me₃Si)^tBuP–P=P(Me)^tBu₂ with PR₃ ^tBu₂P–P=P(Me)^tBu₂ ( 1 ) reacts at 20 °C with PMe₃, PEt₃, P(c‐Hex)₃, P(p‐Tol)₃, PPh₂Me, PPh₂Et, PPhEt₂, PPh₂ⁱPr, PPh₃ and P(NEt₂)₃ yielding ^tBu₂P–P=PR₃ and ^tBu₂PMe; however, P^tBu₃, P^tBu₂(SiMe₃) and ^tBu₂PCl don't. ^tBu₂PH and 1 form ^tBu₂P–PH–P^tBu₂ which yields ^tBu₂P–P=PEt₃ when treated with PEt₃. Ph₂PH, ^tBuPH₂, PH₃, Ph₂PCl and EtOH don't substitute the ^tBu₂PMe group in 1 , instead, the molecule is decomposed. With PEt₃, (Me₃Si)^tBuP–P=P(Me)^tBu₂ forms (Me₃Si)^tBuP–P=PEt₃. The compounds ^tBu₂P–P=PR₃ decompose at 20 °C to different degrees giving P‐rich consecutive products of the phosphinophosphinidene.     

Die Kristallstruktur des tBu2P?PP(Br)tBu2

The Crystal Structure of tBu₂P? P?P(Br)tBu₂ tBu₂P? P?P(Br)tBu₂ 1 crystallizes in the monoclinic space group P2₁/c with a = 2 888.9(3), b = 972.16(10), c = 1 534.04(14) pm, β = 105.129(8)° and 8 formula units in the unit cell. The two independent P₃-units in 1 form angles of 105.77° or 105.98°, resp. One P? P distance (220,4 pm) corresponds to a single bond, the other one (207.9 pm) to a double bond.     

Über Bildung und Reaktionen der CH2Li‐Derivate von tBu2P–P=P(CH3)tBu2 und (Me3Si)tBuP–P=P(CH3)tBu2

Formation and Reactions of the CH₂Li‐Derivatives of ^tBu₂P–P=P(CH₃)^tBu₂ and (Me₃Si)^tBuP–P=P(CH₃)^tBu₂ With ⁿBuLi, (Me₃Si)^tBuP–P=P(CH₃)^tBu₂ ( 1 ) and ^tBu₂P–P=P(CH₃)^tBu₂ ( 2 ) yield (Me₃Si)^tBuP–P=P(CH₂Li)^tBu₂ ( 3 ) and ^tBu₂P–P=P(CH₂Li)^tBu₂ ( 4 ), wich react with Me₃SiCl to give (Me₃Si)^tBuP–P=P(CH₂–SiMe₃)^tBu₂ ( 5 ) and ^tBu₂P–P=P(CH₂–SiMe₃)^tBu₂ ( 6 ), respectively. With ^tBu₂P–P(SiMe₃)–P^tBuCl ( 7 ), compound 3 forms 5 as well as the cyclic products [H₂C–P(^tBu)₂=P–P(^tBu)–P^tBu] ( 8 ) and [H₂C–P(^tBu)₂=P–P(P^tBu₂)–P(^tBu)] ( 9 ). Also 3 forms 8 with ^tBuPCl₂. The cleavage of the Me₃Si–P‐bond in 1 by means of C₂Cl₆ or N‐bromo‐succinimide yields (Cl)^tBuP–P=P(CH₃)^tBu₂ ( 10 ) or (Br)^tBuP–P=P(CH₃)^tBu₂ ( 11 ), resp. With LiP(SiMe₃)₂, 10 forms (Me₃Si)₂P–P(^tBu)–P=P(CH₃)^tBu₂ ( 12 ), and Et₂P–P(^tBu)–P=P(CH₃)^tBu₂ ( 13 ) with LiPEt₂. All compounds are characterized by ³¹P NMR Data and mass spectra; the ylide 5 and the THF adduct of 4 additionally by X‐ray structure analyses.     

Bildung und Strukturen von [{η2‐tBu2P–P=P–PtBu2}Pt(PR3)2]

Coordination Chemistry of P‐rich Phosphanes and Silylphosphanes. XVIII. Syntheses and Structures of [{η²‐^tBu₂P–P=P–P^tBu₂}Pt(PR₃)₂] ^tBu₂P–P=P(Me)^tBu₂ reacts with [{η²‐C₂H₄} · Pt(PR₃)₂] as well as with [{η²‐^tBu₂P–P}Pt(PR₃)₂] yielding [{η²‐^tBu₂P–P=P–P^tBu₂}Pt(PR₃)₂]; PR₃ = PMe₃ 3 a , PEtPh₂ 3 b , 1/2 dppe 3 c , PPh₃ 3 d , P(p‐Tol)₃ 3 e . All compounds are characterized by ¹H and ³¹P NMR spectra, for 3 b and 3 d also crystal structure determinations were performed. 3 b crystallizes in the triclinic space group P1 (No. 2) with a = 1212.58(7), b = 1430.74(8), c = 1629.34(11) pm, α = 77.321(6), β = 70.469(5), γ = 87.312(6)°. 3 d crystallizes in the triclinic space group P1 (No. 2) with a = 1122.60(9), b = 1355.88(11), c = 2025.11(14) pm, α = 83.824(9), β = 82.498(9), γ = 67.214(8)°.     

Komplexchemie P-reicher Phosphane und Silylphosphane. XIV. Phosphinophosphiniden tBu2P?P als Ligand in den Pt-Komplexen [η2-{tBu2P?P}Pt(PPh3)2] und [η2-{tBu2P?P}Pt(PEtPh2)2]

Coordination Chemistry of P-rich Phosphanes and Silylphasphanes. XIV. The Phosphinophosphinidene ^tBu₂P? P as a Ligand in the Pt Complexes [η²-{^tBu₂P? P}Pt(PPh₃)₂] and [η²-{^tBu₂P? P}Pt(PEtPh₂)₂] [η²-{^tBu₂P? P}Pt(PPh₃)₂ 1 and [η²-{^tBu₂P? P}Pt(PEtPh₂)₂] 2 are the first complex compounds of ^tBu₂P? P 5 . They are formed in the reaction of ^tBu₂P? P ? P(Me)^tBu₂ 3 with [η²-{H₂C ? CH₂}Pt(PPh₃)₂] 6 or [η²-{H₂C ? CH₂}Pt(PEtPh₂)₂] 7 , respectively. Compound 1 is less stable than 2 and reacts on to [η²-{^tBu₂P? P} Pt(PPh₃)(P^tBu₂Me)] 10 with the coincidently formed ^tBu₂PMe. The molecular structures of 1 and 2 were derived from their ¹H and ³¹P-NMR spectra, 2 was additionally characterized by a X ray structure determination. 2 crystallizes in the monoclinic space group P2₁/n with a = 1222.36(7) pm, b = 1770.7(1) pm, c = 1729.7(1) pm, β = 108.653(6)°.     

Heterodinukleare Komplexe: Synthese und Kristallstrukturen von [RuRh(μ‐CO)(CO)4(μ‐PtBu2)(tBu2PH)], [RuRh(μ‐CO)(CO)3(μ‐PtBu2)(μ‐Ph2PCH2PPh2)] und [CoRh(CO)4(μ‐H)(μ‐PtBu2)(tBu2PH)]

Heterobinuclear Complexes: Synthesis and X‐ray Crystal Structures of [RuRh(μ‐CO)(CO)₄(μ‐P^tBu₂)(^tBu₂PH)], [RuRh(μ‐CO)(CO)₃(μ‐P^tBu₂)(μ‐Ph₂PCH₂PPh₂)], and [CoRh(CO)₄(μ‐H)(μ‐P^tBu₂)(^tBu₂PH)] [Ru₃Rh(CO)₇(μ₃‐H)(μ‐P^tBu₂)₂(^tBu₂PH)(μ‐Cl)₂] ( 2 ) yields by cluster degradation under CO pressure as main product the heterobinuclear complex [RuRh(μ‐CO)(CO)₄(μ‐P^tBu₂)(^tBu₂PH)] ( 4 ). The compound crystallizes in the orthorhombic space group Pcab with a = 15.6802(15), b = 28.953(3), c = 11.8419(19) Å and V = 5376.2(11) ų. The reaction of 4 with dppm (Ph₂PCH₂PPh₂) in THF at room temperature affords in good yields [RuRh(μ‐CO)(CO)₃(μ‐P^tBu₂)(μ‐dppm)] ( 7 ). 7 crystallizes in the triclinic space group P 1 with a = 9.7503(19), b = 13.399(3), c = 15.823(3) Å and V = 1854.6 ų. Moreover single crystals of [CoRh(CO)₄(μ‐H)(μ‐P^tBu₂)(^tBu₂PH)] ( 9 ) could be obtained and the single‐crystal X‐ray structure analysis revealed that 9 crystallizes in the monoclinic space group P2₁/a with a = 11.611(2), b = 13.333(2), c = 18.186(3) Å and V = 2693.0(8) ų.     

Bildung und Struktur des iso-Tetraphosphans P(PtBu2)3: ein Molekül mit einem planaren,dreibindigen P-Atom

Formation and Structure of the iso -Tetraphosphane P(P^tBu₂)₃: a Molecule with a Planar Three-coordinated P Atom The iso-tetraphosphane P(P^tBu₂)₃ ( 1 ) was obtained by irradiating ^tBu₂P–P=P(Me)^tBu₂ ( 3 ). 1 forms hexagonal crystals (space group P6₃/m) with a = 1005,63(8), c = 1621,4(2) pm, Z = 2. The P(P^tBu₂)₃ molecules are arranged in a hexagonally close packed lattice. The four P atoms in each molecule are coplanar with P–P bond distances 219.08(4) pm and P–P–P angles 120°. The observed planar geometry is in accordance with ab initio calculations.     

Komplexchemie P-reicher Phosphane und Silylphosphane. XI [1]. Bildung,Reaktionen und Strukturen von Chromcarbonylkomplexen aus Reaktionen von Li(THF)2[η2-(tBu2P)2P] mit Cr(CO)5 · THF und Cr(CO)4 · NBD

Transition Metal Complexes of P-rich Phosphanes and Silylphosphanes. XI. Formation, Reactions, and Structures of Chromium Carbonyl Complexes from Reactions of Li(THF)₂[η₂-(^tBu₂P)₂P] with Cr(CO)₅ · THF and Cr(CO)₄ · NBD Reactions of Li(THF)₂[η²-(^tBu₂P)₂P] 1 with Cr(CO)₅ · THF yield Li(THF)₂Et₂O[Cr(CO)₄{η²-(^tBu₂P)₂P}η¹-Cr(CO)₅] 2 and the compounds [Cr(CO)₄{η²-(^tBu₂P)₂PH}] 3 , [Cr(CO)₅{η¹-(^tBu₂P)₂PH}] 4 , (^tBu₂P)₂PH 5 and ^tBu₂PH · Cr(CO)₅ 6 . The formation of 3, 4, 5 and 6 is due to byproducts coming from the synthesis of 1. 2 reacts with CH₃COOH under formation of 3 . After addition of 12-crown-4 1 with NBD · Cr(CO)₄ in THF forms Li(12-crown-4)₂[Cr(CO)₄-{η²-(^tBu₂P)₂P}] 7 (yellow crystals). 7 reacts with CH₃COOH to 3 – which regenerates 7 with LiBu – with Cr(CO)₅THF to compound 2 , with NBD · Cr(CO)₄ in THF to 2 and 3 (ratio 1 : 1). With EtBr, 7 forms [Cr(CO)₄{η²-(^tBu₂P)₂PEt}] 8 , and [Cr(CO)₄{η²-(^tBu₂P)₂PBr}] 9 with BrCH₂? CH₂Br. The compounds were characterized by means of ¹H, ¹³C, ³¹P, ⁷Li NMR spectroscopy, IR spectroscopy, elementary analysis, mass spectra, and 2, 3 and 4 additionally by means of X-ray diffraction analysis. 2 crystallizes in the space group P1 with 2 formula units in the elementary cell; a = 10.137(9), b = 15.295(12), c = 15.897(14) Å; α = 101.82(7), β = 91.65(7), γ = 98.99(7)°; 3 crystallizes in the space group P2_t/n with 4 molecules in the elementary unit; a = 11.914(6), b = 15.217(10), c = 14.534(10) Å; α = 90, β = 103.56(5), γ = 90°. 4 : space group P1 with 2 molecules in the elementary unit; a = 8.844(4), b = 12.291(6), c = 14.411(7) Å, α = 66.55(2), β = 89.27(2), γ = 71.44(2)°.     

tBu2P?PP(X)tBu2-Ylide (X = Cl,Br, I) durch Halogenierung von [tBu2P]2P?SiMe3

tBu₂P? P?P(X)tBu₂ Ylides (X = Cl, Br, I) by Halogenation of [tBu₂P]₂P? SiMe₃ [tBu₂P]₂P? SiMe₃ 1 with halogenating agents as Br₂, I₂, Br-succinimide, CCl₄, CBr₄, CI₄ or C₂Cl₆ via cleavage of the Si? P bond in 1 produces the ylides tBu₂P? P?P(X)tBu₂ (X = Cl, Br, I). This proceeds independent from the formerly known pathway – [tBu₂P]₂PLi + 1,2-dibromoethane – and shows that the Li-phosphide must not be present as a necessary requirement for the formation of ylides.     

Die Bildung von [(tBu)2P]2P?P[P(tBu)2]2 aus LiP[P(tBu)2]2 und 1,2-Dibromethan. Die Thermolyse von tBu2P?PP(Br)tBu2

[(tBu)₂P]₂P? P[P(tBu)₂]₂ from LiP[P(tBu)₂]₂ and 1,2-Dibromomethane. Pyrolysis of tBu₂P? P?P(Br)tBu₂ All products of the reaction of [tBu₂P]₂PLi 1 with 1,2-dibromoethane 2 were investigated. Already at ?70°C tBu₂P? P?P(Br)tBu₂ 3 as main product and [tBu₂P]₂PBr 4 are formed. Only with an excess of 1 also [tBu₂P]P? P[P(tBu)₂]₂ 5 is obtained. Warming of a pure solution of 3 in toluene from ?70°C to ?30°C leads to 4 , and at 20°C tBu₂PBr and the cyclophosphanes P₄[P(tBu)₂]₄ and P₃[P(tBu)₂]₃ are observed. 5 does not result from 3 , it's rather a byproduct from the reaction of 1 with 4 . Also the ylide 3 and 1 yields 5 .     

Synthesis of the New Silanediyldiphosphinite tBu2Si(OPPh2)2 and its Reactions with the Norbornadiene Complexes C7H8M(CO)4 (M = Cr,Mo, W). Crystal Structures of cis-M(CO)4[tBu2Si(OPPh2)2] (M = Cr,Mo)

Silanediyldiphosphinite tBu₂Si(OPPh₂)₂ 1 has been synthesised. 1 reacts with the norbornadiene complexes C₇H₈M(CO)₄ (M = Cr, Mo, W) to give six-membered chelate rings of the type cis-M(CO)₄[tBu₂Si(OPPh₂)₂] 2–4 . The crystal structures of the chromium and molybdenum complexes cis-Cr(CO)₄[tBu₂Si(OPPh₂)₂] 2 and cis-Mo(CO)₄[tBu₂Si(OPPh₂)₂] 3 have been determined. Both complexes crystallise in the triclinic system (space group P1 ) with unit cell parameters: ( 2 ) a = 1 093(3) pm, b = 1 477(5) pm and c = 1 542(5) pm; α = 108.4(2)°, b? = 103.87(11)° and b? = 104.57(10)°; U = 2.143(12) nm³; Z = 2; ( 3 ) a = 1 097.8(2) pm, b = 1 483.7(2) pm and c = 1 554.3(2) pm; α = 108.10(1)°, b? = 103.956(6)° and γ = 104.213(7)°; U = 2.1899(6) nm³; Z = 2. Both 2 and 3 consist of discrete, slightly distorted, octahedral monomers in which the six-membered chelate rings are essentially planar. In contrast, the conformations of the chelate rings found in crystal structures of analogous complexes vary from twist-boat to “chaise longue”.     

Reactions of tBu2P–PLi–PtBu2 with [(Et3P)2MCl2] (M = Ni,Pd, Pt). Synthesis and Properties of [(1,2‐η‐tBu2P=P–PtBu2)M(PEt3)Cl] (M=Ni,Pd)

^tBu₂P–PLi–P^tBu₂·2THF reacts with [cis‐(Et₃P)₂MCl₂] (M = Ni, Pd) yielding [(1,2‐η‐^tBu₂P=P–P^tBu₂)Ni(PEt₃)Cl] and [(1,2‐η‐^tBu₂P=P–P^tBu2)Pd(PEt₃)Cl], respectively. ^tBu₂P– PLi–P^tBu₂ undergoes an oxidation process and the ^tBu₂P–P–P^tBu₂ ligand adopts in the products the structure of a side‐on bonded 1,1‐di‐tert‐butyl‐2‐(di‐tert‐butylphosphino)diphosphenium cation with a short P–P bond. Surprisingly, the reaction of ^tBu₂P–PLi–P^tBu₂·2THF with [cis‐(Et₃P)₂PtCl₂] does not yield [(1,2‐η‐^tBu₂P=P–P^tBu₂)Pt(PEt₃)Cl].     

Reaktionen von (tBu)2P?PP(Br)tBu2 mit LiP(SiMe3)2, LiPMe2 und LiMe,LitBu, LinBu

Reactions of (tBu)₂P? P?P(Br)tBu₂ with LiP(SiMe₃)₂, LiPMe₂ and LiMe, LitBu and LinBu The reactions of (tBu)₂P? P?P(Br)tBu₂ 1 with LiP(SiMe₃)₂ 2 yield (Me₃Si)₂P? P(SiMe₃)₂ 4 and P[P(tBu)₂]₂P(SiMe₃)₂ 5 , whereas 1 with LiPMe₂ 2 yields P₂Me₄ 6 and P[(tBu)₂]₂PMe₂ 7 . 1 with LiMe yields the ylid tBu₂P? P?P(Me)tBu₂ (main product) and [tBu₂P]₂PMe 15 . In the reaction of 1 with tBuLi [tBu₂P]₂PH 11 is the main product and also tBuP? P?P(R)tBu₂ 21 is formed. The reaction of 1 with nBuLi leads to [tBu₂P]₂PnBu 17 (main product) and tBu₂P? P?P(nBu)tBu₂ 22 (secondary product).     

Bildung und Struktur des [{η2‐tBu2P–P}Pt(PHtBu2)(PPh3)]

Coordination Chemistry of P‐rich Phosphanes and Silylphosphanes. XX Formation and Structure of [{η²‐^tBu₂P–P}Pt(PH^tBu₂)(PPh₃)] [{η²‐^tBu₂P¹–P²}Pt(P³Ph₃)(P⁴Ph₃)] ( 2 ) reacts with ^tBu₂PH exchanging only the P³Ph₃ group to give [{η²‐^tBu₂P¹–P²}Pt(P³H^tBu₂)(P⁴Ph₃)] ( 1 ). The crystal stucture determination of 1 together with its ³¹P{¹H} NMR data allow for an unequivocal assignment of the coupling constants in related Pt complexes. 1 crystallizes in the triclinic space group P1 (no. 2) with a = 1030.33(15), b = 1244.46(19), c = 1604.1(3) pm, α = 86.565(17)°, β = 80.344(18)°, γ = 74.729(17)°.