Synthesis and Crystal Structure of a Tetranuclear Molybdenum(II) Silylamido Cluster

Treatment of molybdenum(II) chloride with the difunctional silylamide Li₂Me₂Si(NPh)₂ led to the formation of the tetranuclear cluster compound [Mo₄{Me₂Si(NPh)₂}₄]. According to the X-ray crystal structure determination, the central core of the cluster consists of four molybdenum atoms in a nearly rectangular arrangement. There are two μ₄-κ-N,N,N',N'-Me₂Si(NPh)₂^2– ligands capping the Mo₄ rectangle and two μ₂-Me₂Si(NPh)₂^2– ligands located at opposite edges. The alternating Mo–Mo distances of 218.1(1) and 279.5(1) pm indicate the presence of a cyclobutadiyne type cluster with alternating Mo–Mo triple and single bonds.     

Copper(I) Clusters with Trifunctional Silyl Amide Ligands. Synthesis and Crystal Structures of [Li(THF)4]2[Cu10{RSi(NPh)3}4] (R = Me,Ph, Vin)

Treatment of CuCl with the lithiated silyl amides RSi(NLiPh)₃ (R = Me, Ph, Vin) in THF as solvent led to the formation of the novel Cu^I cluster compounds [Li(THF)₄]₂[Cu₁₀{RSi(NPh)₃}₄]. For each of the three compounds the X‐ray crystal structure analysis revealed similar Si₄N₁₂Cu₁₀ cores which are based on cubane like Cu₈ cores bearing two additional peripheral copper atoms. The copper atoms are coordinated nearly linearly by the μ₅‐bridging silyl amide ligands with Cu–N distances in the range of 187.1(3) to 194.5(4) pm and N–Cu–N angles of 171.6(1) to 178.7(1)°. For each of the compounds the structural parameters are very similar which indicates that the structures are barely influenced by the different steric requirements of the organic groups bound to silicon.     

Synthesis and Crystal Structures of Aluminum,Gallium and Indium Complexes with Chelating Me2Si(NPh)22– Ligands

The reaction of ECl₃ (E = Al, Ga) with two equivalentsof Li₂Me₂Si(NPh)₂ (in diethyl ether/n‐hexane) leads to the formation of bis‐chelate complexes [Li(OEt₂)₃][E{Me₂Si(NPh)₂}₂] (E = Al ( 1 ), Ga ( 2 )). Compounds 1 and 2 crystallize isotypically in the monoclinic system with a = 1136.42(6), b = 3267.9(1), c = 1360.37(8) pm, β = 94.320(7)° for 1 and a = 1140.88(6), b = 3261.7(2), c = 1360.20(8) pm, β = 94.641(7)° for 2 . Both the compounds display a distorted tetrahedral coordination of the central metal atom to give a spirocyclic EN₄Si₂ core. The Al–N bond lengths are in the range of186.5–186.9 pm and for the Ga–N distances values between 192.3and 193.1 pm are observed. Treatment of InCl₃ with three equivalents of Li₂Me₂Si(NPh)₂ yields the tris‐chelate [{Li(OEt₂)}₃In{Me₂Si(NPh₂)}₃] 3 . Compound 3 crystallizes in the trigonal crystal system , space group R$\bar{3}$ c with a = 1852.4(1), and c = 3300.2(2) pm. The central indium atom is coordinated by threeMe₂Si(NPh)₂^2– ligands in a distorted octahedral arrangement withIn–N bond lengths of 230.8 pm.     

Synthese und spektroskopische Charakterisierung einiger Pentacarbonylwolfram(0)‐Komplexe mit monound bicyclischen Phosphiran‐Liganden: Kristallstruktur von [{(Me3Si)2HCPC(H)H–C(H)Ph}W(CO)5]

Synthesis and Spectroscopic Characterisation of some Pentacarbonyltungsten(0) Complexes with Mono‐ and Bicyclic Phosphirane Ligands: Crystal Structure of [{(Me₃Si)₂HCPC(H)H–C(H)Ph}W(CO)₅] The tungsten(0) complex [{(Me₃Si)₂HCPC(Ph)=N}W(CO)₅] ( 1 ) reacts upon heating with alkene derivatives 2 , 6 , 8 , and 10 in toluene to form benzonitrile and the complexes [{(Me₃Si)₂HCPC(R¹,R²)–C(R³,R⁴}W(CO)₅] ( 4 , 7 a , b , 9 a , b , 11 a , b ) ( 4 (trans): R¹,R³ = Ph, R²,R⁴ = H, 7 a , b (cis, meso and rac): R¹,R³ = Ph, R²,R⁴ = H, 9 a , b (RR und SS): R¹ = Ph, R²,R³,R⁴ = H, 11 a , b : R¹=R³ = (CH₂)₄, R²,R⁴ = H). Spectroscopic and mass spectrometric data are discussed. The structure of the complex 9 a was determined by X‐ray single crystal structure analysis showing characteristic data for the phosphirane ring such as a narrow angle at phosphorus (49,2(2)°), different P–C distances (P–C(6) 182,1(5) and P–C(7) 185,2(4) pm) and 152,9(6) pm for the basal C–C bond.     

Hydroalumination and Hydrogallation Reactions with Tri(ethynyl)silanes – Generation of Compounds with up to Three Coordinatively Unsaturated Aluminium Atoms

Hydroalumination or hydrogallation of tri(ethynyl)silanes, RSi(C≡C‐Ar)₃ ( 1a , R = Ph, Ar = Ph; 1b , R = Me, Ar = Ph; 1c , R = Me, Ar = C₆H₄Me), with the element hydrides H‐EtBu₂ (E = Al, Ga) in stoichiometric ratios of 1:1 to 1:3 at ambient temperature yielded the addition products (PhC≡C)₂(R)Si[(tBu₂E)C=C(H)Ph] ( 2 , R = Ph, E = Ga; 3a , R = Me, E = Al; 3b , R = Me, E = Ga), (PhC≡C)(Me)Si[(tBu₂E)C=C(H)Ph]₂ ( 4a , E = Al, 4b , E = Ga) and (Me)Si[(tBu₂Al)C=C(H)Ar]₃ ( 5 , Ar = Ph; 6 , Ar = C₆H₄Me). Compounds 2 – 4 show a relatively close interaction between the coordinatively unsaturated aluminium or gallium atoms and one of the C_α(≡C) atoms of unreacted alkyne substituents [245 (E = Al) and 266 pm (E = Ga)] that stabilises the kinetically favoured cis addition products with E and hydrogen on the same side of the resulting C=C double bonds. In the absence of these stabilising effects the compounds were found to isomerise to the thermodynamically favoured trans isomers.     

Versatile Reactivity of Scorpionate‐Anchored Yttrium?Dialkyl Complexes towards Unsaturated Substrates

A series of unusual chemical‐bond transformations were observed in the reactions of high active yttrium? dialkyl complexes with unsaturated small molecules. The reaction of scorpionate‐anchored yttrium? dibenzyl complex [Tp^Me2Y(CH₂Ph)₂(thf)] ( 1 , Tp^Me2=tri(3,5‐dimethylpyrazolyl)borate) with phenyl isothiocyanate led to C?S bond cleavage to give a cubane‐type yttrium–sulfur cluster, {Tp^Me2Y(μ₃‐S)}₄ ( 2 ), accompanied by the elimination of PhN?C(CH₂Ph)₂. However, compound 1 reacted with phenyl isocyanate to afford a C(sp³)? H activation product, [Tp^Me2Y(thf){μ‐η¹:η³‐OC(CHPh)NPh}{μ‐η³:η²‐OC(CHPh)NPh}YTp^Me2] ( 3 ). Moreover, compound 1 reacted with phenylacetonitrile at room temperature to produce γ‐deprotonation product [(Tp^Me2)₂Y]⁺[Tp^Me2Y(N=C?CHPh)₃]^? ( 6 ), in which the newly formed N?C?CHPh ligands bound to the metal through the terminal nitrogen atoms. When this reaction was carried out in toluene at 120 °C, it gave a tandem γ‐deprotonation/insertion/partial‐Tp^Me2‐degradation product, [(Tp^Me2Y)₂(μ‐Pz)₂{μ‐η¹:η³‐NC(CH₂Ph)CHPh}] ( 7 , Pz=3,5‐dimethylpyrazolyl).     

Darstellung von Organylquecksilber(II)‐di(methansulfonyl)amiden und Kristallstruktur von Ph–Hg–N(SO2Me)2

Polysulfonylamines. CXXIV. Preparation of Organylmercury(II) Di(methanesulfonyl)amides and Crystal Structure of Ph–Hg–N(SO₂Me)₂ Four N,N‐disulfonylated organylmercury(II) amides R–Hg–N(SO₂Me)₂, where R is Me, ⁱPr, Me₃SiCH₂ or Ph, were obtained on treating the appropriate chlorides RHgCl with AgN(SO₂Me)₂, and characterized by ¹H and ¹³C NMR spectra. In the crystal structure of the phenyl compound (orthorhombic, space group Pbca, Z = 8, X‐ray diffraction at –95 °C), the molecule exhibits a covalent and significantly bent C–Hg–N grouping [bond angle 172.7(3)°; Hg–C 204.0(8), Hg–N 209.1(7) pm]. One sulfonyl oxygen atom forms a short intramolecular Hg…O contact [296.1(5) pm] and simultaneously catenates glide‐plane related molecules via a second Hg…O interaction 297.6(5) pm], thus conferring upon Hg^II the effective coordination number 4 and a geometrically irregular coordination polyhedron (bond angles from 173 to 54°).     

Thallium(I), Silver(I), and Mixed Thallium(I)/Copper(I) Clusters with Bridging {Me2Si(N‐C6H4‐2‐SPh)2}2– Ligands

The S‐functionalized aminosilane Me₂Si(NH‐C₆H₄‐2‐SPh)₂ (H₂L) ( 1 ) was prepared from dichlorodimethylsilane and lithiated 2‐(phenylthio)aniline. Treatment of compound 1 with two equivalents of n‐butyllithium led to the dilithium derivative Li₂L, which was used in subsequent reactions with MCl (M = Tl, Cu, Ag) to prepare the complexes [Tl₂L] ( 2 ), [Cu₂Tl₂L₂] · 2THF ( 3a ), [Cu₂Tl₂L₂(THF)₂] ( 3b ), and [Ag₄L₂(THT)₂] ( 4 ) (THT = tetrahydrothiophene). Compound 2 consists of two thallium atoms, which are connected by a L^2– ligand to give a puckered Tl₂N₂ ring with Tl–N distances of 255(1)–268(1) pm. Compounds 3a and 3b are heterobimetallic complexes, which are based on [Cu₂L₂]^2– cores featuring a Cu₂N₄Si₂ ring with linearly coordinated copper atoms [Cu–N: 190.7(3)–192.5(3) pm] and two peripherally attached Tl atoms [Tl–N: 272.7(3)–281.9(3) pm]. The molecular structure of the tetranuclear silver(I) complex 4 is closely related to the structure of compounds 3a and 3b by replacement of the Cu and Tl atoms with Ag atoms. The Ag–N distances are 217.5(3)–245.7(3) pm.     

Nd3Si5AlON10 – Synthese,Kristallstruktur und Eigenschaften eines Sialons im La3Si6N11‐Strukturtyp

Nd₃Si₅AlON₁₀ – Synthesis, Crystal Structure, and Properties of a Sialon Isotypic with La₃Si₆N₁₁ Nd₃Si₅AlON₁₀ was synthesized by the reaction of silicon diimide, aluminium nitride, aluminium oxide, and neodymium in a pure nitrogen atmosphere at 1650 °C using a radiofrequency furnace. The compound was obtained as a coarsely crystalline solid. According to the single‐crystal structure determination the title compound is isotypic with Ln₃Si₆N₁₁ (Ln = La, Ce, Pr, Nd, Sm). Nd₃Si₅AlON₁₀ (P4bm, a = 1007.8(1), c = 486.3(1) pm, Z = 2, R₁ = 0.016, wR₂ = 0.031) is built up by a three‐dimensional network structure of corner sharing SiON₃ and (Si/Al)N₄ tetrahedra (molar ratio Si : Al = 3 : 1). According to lattice energetic calculations using the MAPLE concept a differentiation of O and N seems to be reasonable. One of the two different sites for the tetrahedral centres is probably occupied by Si (distances: Si–O: 168.4(1), Si–N: 173.6(3)–176.0(4) pm) the second site by Si and Al with the molar ratio 3 : 1 (distances: (Si/Al)–N: 172.0(3)–176.6(2) pm). The Nd³⁺ ions are located in the voids of the (Si₅AlON₁₀)^9– framework (distances: Nd–O: 261.07(8), Nd–N: 246.1(2)–286.6(2) pm).     

Synthese und spektroskopische Charakterisierung einiger Pentacarbonylwolfram(0)-Komplexe mit verschiedenen 1H-Phosphiren-Liganden,Kristallstrukturen von,und

Synthesis and Spectroscopic Characterization of some Pentacarbonyltungsten(0) Complexes with Various 1H-Phosphirene Ligands: Crystal Structures of , and The tungsten(0) complex 1 reacts upon heating with acetylene derivatives 2a–f in toluene to form benzonitrile and the complexes 4a–f ( 4a : R¹ ? Ph, R² ? H; 4b : R¹ ? Ph, R² ? CH₃; 4c : R¹ ? OEt, R² ? H; 4d : R¹ ? Ph, R² ? CO₂Et; 4e : R¹, R² ? CO₂Me; 4f : R¹, R² ? SiMe₃), which have been isolated by chromatography. Spectroscopic and mass spectrometric data are discussed. The crystal structures of the compounds 4a, b and d were determined by X-ray single crystal structure analysis ( 4a : space group P2₁/n, Z = 4, a = 937,5(2) pm, b = 2202,4(6) pm, c = 1266,3(4) pm, β = 108,94(4)°; 4b : space group P2₁/c, Z = 4, a = 1293,9(2) pm, b = 923,5(1) pm, c = 2223,4(3) pm, β = 92,385(6)°; 4d : space group P2₁/c, Z = 4, a = 955,2(2) pm, b = 3190,9(4) pm, c = 930,7(2) pm, β = 99,64(1)°).     

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.     

Isomerism of copper(II) coordination compounds with hydroxamic acids

The structure of Cu^II complexes with hydroxamic acids Cu[R¹N(O)−(O)CR²]₂, where R¹=Ph, R²=Me; R¹=Me, R²=Ph, was studied by ESR spectroscopy. In toluene solutions and low-temperature glasses, the complexes exist as two forms, which were identified ascis-andtrans-isomers. The proportions of the isomers were determined. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 726–729, April, 1999.     

Synthese und Kristallstruktur des Aminoimino‐Phosphinat–Kupfer(I)‐Komplexes [Cu(Me3SiNP(Ph)2NSiMe3)]2

Synthesis and Crystal Structure of the Aminoiminophosphinate Copper(I) Complex [Cu(Me₃SiNP(Ph)₂NSiMe₃)]₂ The title compound 1 was prepared by the reaction of Me₃SiNP(Ph)₂N(SiMe₃)₂ with copper(I) chloride at 120 °C to give colourless crystals which were characterized by a crystal structure determination. Space group C2/c, Z = 4, lattice dimensions at 193 K: a = 1854.0(3), b = 1256.2(3), c = 1969.9(3) pm, β = 106.30(2)°; R₁ = 0.063. 1 forms dimeric molecules with a nonplanar Cu₂N₄P₂ eight‐membered ring of symmetry C₂ and a rather long Cu…Cu distance of 262.1(1) pm.     

Darstellung,Charakterisierung und Struktur funktionalisierter Fluorphosphaalkene des Typs R3E–P=C(F)NEt2 (R/E = Me/Si,Me/Ge,CF3/Ge,Me/Sn)

Preparation, Characterization, and Structure of Functionalized Fluorophosphaalkenes of the Type R₃E–P=C(F)NEt₂ (R/E = Me/Si, Me/Ge, CF₃/Ge, Me/Sn) P‐functionalized 1‐diethylamino‐1‐fluoro‐2‐phosphaalkenes of the type R₃E–P=C(F)NEt₂ [R/E = Me/Si ( 2 ), Me/Ge ( 3 ), CF₃/Ge ( 4 ), Me/Sn ( 5 )] are prepared by reaction of HP=C(F)NEt₂ ( 1 , E/Z = 18/82) with R₃EX (X = I, Cl) in the presence of triethylamine as base, exclusively as Z‐Isomers. 2–5 are thermolabile, so that only the more stable representatives 2 and 4 can be isolated in pure form and fully characterized. 3 and 5 decompose already at temperatures above –10 °C, but are clearly identified by ¹⁹F and ³¹P NMR‐measurements. The Z configuration is established on the basis of typical NMR data, an X‐ray diffraction analysis of 4 and ab initio calculations for E and Z configurations of the model compound Me₃Si–P=C(F)NMe₂. The relatively stable derivative 2 is used as an educt for reactions with pivaloyl‐, adamantoyl‐, and benzoylchloride, respectively, which by cleavage of the Si–P bond yield the push/pull phosphaalkenes RC(O)–P=C(F)NEt₂ [R = tBu ( 6 ), Ad ( 7 ), Ph ( 8 )], in which π‐delocalization with the P=C double bond occurs both with the lone pair on nitrogen and with the carbonyl group.     

Gold(I) and Silver(I) Complexes with Thioether Functionalized Silylamido Ligands

The thioether functionalized aminosilanes Me₂Si(NH‐C₆H₄‐2‐SR)₂ (R = Ph, Me) were lithiated with nBuLi and subsequently reacted with AgCl in the presence of PMe₃ or with [AuCl(PMe₃)]. In the case of Me₂Si(NH‐C₆H₄‐2‐SPh)₂ the dinuclear complexes [M₂{Me₂Si(NC₆H₄‐2‐SPh)₂}(PMe₃)₂] (M = Ag; Au) were isolated. The analogous reactions starting from Me₂Si(NH‐C₆H₄‐SMe)₂ afforded the dinuclear gold complex [Au₂{Me₂Si(NC₆H₄‐2‐SMe)₂}(PMe₃)₂] and the tetranuclear silver complex [Ag₄{Me₂Si(NC₆H₄‐2‐SMe)₂}₂(PMe₃)₂]. In the dinuclear compounds of the type [M₂{Me₂Si(NC₆H₄‐2‐SR)₂}(PMe₃)₂], each of the silylamide N atoms is connected to a M(PMe₃) group to give a nearly linear N–M–P arrangement with Ag–N and Au–N bonds in the range of 212.0(4)–213.3(4) pm and 205.3(3)–208.1(9) pm, respectively. [Ag₄{Me₂Si(NC₆H₄‐2‐SMe)₂}₂(PMe₃)₂] consists of a central Si₂N₄Ag₂ ring with linearly coordinated Ag atoms (Ag‐N: 223.1(4)–222.1(4) pm) and two peripheral Ag(PMe₃) units, which are connected to the amido N atoms in a chelating mode. The relatively short transannular Ag ··· Ag separation (277.6(1) pm) within the Si₂N₄Ag₂ ring hints for argentophilic interactions. The peripheral Ag atoms are three coordinated with Ag–N distances of 233.9(4)–242.8(4) pm.     

Die ersten Bor(III)-di(organosulfonyl)amide: Ein neuartiger B(OS)2N-Sechsring und zwei Aminoboran-Strukturen mit langen B–N-Bindungen

Polysulfonylamines. XCIX. The First Boron(III) Di(organosulfonyl)amides: A Novel B(OS)₂N Six-Membered Ring and Two Aminoborane Structures with Long B–N Bonds Ph₂B[N(SO₂Me)₂] ( 1 ) and the benzo-1,3,2-dioxaboroles C₆H₄O₂BN(SO₂R)₂, where R = Ph ( 2 a ) or Me ( 2 b ), were prepared by treating the appropriate bromoboranes with Me₃SiN(SO₂Me)₂ and/or AgN(SO₂R)₂. Their crystal and molecular structures were determined by low-temperature X-ray diffraction ( 1 : monoclinic, space group P2₁/n; 2 a : monoclinic, P2₁/c; 2 b : triclinic, P 1, structure marred by disorder of one MeSO₂ group). The B atom of 1 features a distorted tetrahedral coordination formed by the ipso-C atoms of the Ph groups and two O atoms of the 1,5-chelating (MeSO₂)₂N⁷ anion (B–O 156.5, 157.7 pm). The resulting six-membered B(OS)₂N ring adopts a boat conformation, B and N lying out of the plane of the other four atoms. In the chelate ligand, which is severely distorted from the common pseudo-C₂ symmetry of the discrete anion, extremely long S–O(B) bonds (151.2, 151.7 pm) are compensated by short N–S bonds (156.1, 156.8 pm). Molecules 2 a and 2 b have aminoborane structures with trigonal-planar coordinations at B and N, unusually long B–N distances suggesting single bonds [ 2 a : 147.6(3), 2 b : 146.3(5) pm], and fairly short N–S bonds ( 2 a : av. 167.4, 2 b : av. 170.4 pm). In 2 a the O₂B plane is twisted by 70.9° vs. the NS₂ plane, whereas the O₂B–NS₂ moiety of 2 b is approximately coplanar (twist-angle ca. 9°).     

Novel Copper(I) Clusters with 2‐(Diphenylphosphanyl)anilide Ligands. Synthesis and Crystal Structures of [Cu6X2(NHR)4] (X = Cl,Br, I; R = C6H4‐2‐PPh2)

Treatment of copper(I) halides CuX (X = Cl, Br, I) with lithium 2‐(diphenylphosphanyl)anilide [Li(HL)] in THF led to the formation of hexanuclear copper(I) complexes [Cu₆X₂(HL)₄] [X = Cl ( 1 ), Br ( 2 ), I ( 3 )]. In compounds 1 – 3 , the copper atoms are in a distorted octahedral arrangement and the amide ligands adopt a μ₃‐κP,κ²N bridging mode. Additionally there are two μ₂‐bridging halide ligands. Each of the [Cu₆X₂(HL)₄] clusters comprises two copper atoms, which are surrounded by two amide nitrogen atoms in an almost linear coordination [Cu–N: 186.2(3)–188.0(3) pm] and four copper atoms, which are connected to an amide N atom, a P atom, and a halogen atom in a distorted trigonal planar fashion [Cu–N: 199.6(3)–202.3(3) pm)].     

P‐Aminophosphaalkenes with C‐Isopropyldimethylsilyl Groups

Amination of the C‐isopropyldimethylsilyl P‐chlorophosphaalkene (iPrMe₂Si)₂C=PCl ( 1 ) leads to the P‐aminophosphaalkenes (iPrMe₂Si)₂C=PN(R)R′ (R, R′ = Me ( 2 ), R = H, R′ = nPr ( 3 ), R = H, R′ = iPr ( 4 ), R = H, R′ = tBu ( 5 ), R = H, R′ = 1‐Ada ( 6 ), R = H, R′ = CPh₃ ( 7 ), R = H, R′ = Ph ( 8 ), R = H, RR′ = 2,6‐iPr₂Ph (= DIP) ( 10 ), R = H, R′ = 2,4,6‐Me₃Ph (= Mes) ( 11 ), R = H, R′ = 2,4,6‐tBu₃Ph (= Mes*)] ( 12 ), R = H, R′ = SiMe₃ ( 13 ), and R, R′ = SiMe₂Ph (1 4 ). ³¹P‐NMR spectra confirm that phosphaalkenes 2 – 7 and 10 – 14 are monomeric in solution; the structures of 7 , 10 , and 12 were determined by X‐ray crystallography. Freshly prepared (iPrMe₂Si)₂C=PN(H)Ph ( 8 ) is a monomer that dimerizes with (N→C) proton migration within several hours to the stable diazadiphosphetidine [(iPrMe₂Si)₂CHPNPh]₂ ( 9 ). NMR‐scale reactions of deprotonated 5 and 13 with tBuiPrPCl provide by P–P bond formation the P‐phosphanyl iminophosphoranes [(iPrMe₂Si)₂C=](RN=)PPtBu(iPr) [R = tBu ( 15 ), R = Me₃Si ( 17 )]. Deprotonated 5 and Me₃GeCl deliver by N–Ge bond formation the aminophosphaalkene (iPrMe₂Si)₂C=PN(tBu)GeMe₃ ( 20 ), which with elemental selenium 5 undergoes (N→C) proton migration to form the alkyl(imino)(seleno)phosphorane [(iPrMe₂Si)₂CH](tBuN=)P=Se ( 21 ), which is a selenium‐bridged cyclic dimer in the solid state.     

Light‐Induced Rearrangement of Thioether‐Substituted Phosphanide Ligands: Scope and Limitations of a Remarkable Isomerization

Treatment of the thioether‐substituted secondary phosphanes R²PH(C₆H₄‐2‐SR¹) [R²=(Me₃Si)₂CH, R¹=Me ( 1_PH ), iPr ( 2_PH ), Ph ( 3_PH ); R²=tBu, R¹=Me ( 4_PH ); R²=Ph, R¹=Me ( 5_PH )] with nBuLi yields the corresponding lithium phosphanides, which were isolated as their THF ( 1 – 5_Pa ) and tmeda ( 1 – 5_Pb ) adducts. Solid‐state structures were obtained for the adducts [R²P(C₆H₄‐2‐SR¹)]Li(L)_n [R²=(Me₃Si)₂CH, R¹=nPr, (L)_n=tmeda ( 2_Pb ); R²=(Me₃Si)₂CH, R¹=Ph, (L)_n=tmeda ( 3_Pb ); R²=Ph, R¹=Me, (L)_n=(THF)_1.33 ( 5_Pa ); R²=Ph, R¹=Me, (L)_n=([12]crown‐4)₂ ( 5_Pc )]. Treatment of 1_PH with either PhCH₂Na or PhCH₂K yields the heavier alkali metal complexes [{(Me₃Si)₂CH}P(C₆H₄‐2‐SMe)]M(THF)_n [M=Na ( 1_Pd ), K ( 1_Pe )]. With the exception of 2_Pa and 2_Pb , photolysis of these complexes with white light proceeds rapidly to give the thiolate species [R²P(R¹)(C₆H₄‐2‐S)]M(L)_n [M=Li, L=THF ( 1_Sa , 3_Sa – 5_Sa ); M=Li, L=tmeda ( 1_Sb , 3_Sb – 5_Sb ); M=Na, L=THF ( 1_Sd ); M=K, L=THF ( 1_Se )] as the sole products. The compounds 3_Sa and 4_Sa may be desolvated to give the cyclic oligomers [[{(Me₃Si)₂CH}P(Ph)(C₆H₄‐2‐S)]Li]₆ (( 3_S )₆) and [[tBuP(Me)(C₆H₄‐2‐S)]Li]₈ (( 4_S )₈), respectively. A mechanistic study reveals that the phosphanide–thiolate rearrangement proceeds by intramolecular nucleophilic attack of the phosphanide center at the carbon atom of the substituent at sulfur. For 2_Pa / 2_Pb , competing intramolecular β‐deprotonation of the n‐propyl substituent results in the elimination of propene and the formation of the phosphanide–thiolate dianion [{(Me₃Si)₂CH}P(C₆H₄‐2‐S)]^2?.     

Reactions of β-nitrostyrenes with tert-butylmercury halides in the presence of lodide lon

Photolysis of t-BuHgCl/KI with PhC(R²)C(R¹)NO₂ forms PhC(R²)C(R¹)Bu-t when R¹ = R² = H or in low yield when R¹ = H, R² = Ph. When R¹ ≠ H, or when R² = Ph, reactions with t-BuHgI/KI/hv proceed mainly via PhC(R²)C(R¹)NO₂·-, PhC(R²)C(R¹)N(OBu-t)O⁻HgX⁺, PhC(R²)C(R¹)NO and PhC(R²)C(R¹)N(OBu-t)HgX to form a variety of novel products including the dimeric bisnitronic esters ( 6 ) with R¹ = Me or Ph and R² = H; PhCH(R²)C(R¹) = NOBu-t with R¹ = Me or Ph and R² = H or R¹ = H and R² = Ph; PhC(R²)(OBu-t)C(R¹)NOH with R¹ = H or Me and R² = Ph; and 3-phenyl-2-R¹-indoles with R¹ = H, Me, Ph, PhS or t-BuS and R² = Ph. Nitrosoaromatics react with t-BuHgX in the dark to form ArN(OBu-t)(OBu-t)HgX⁺ which condenses with ArNO to form the azoxy compound. tert-Butyl radicals will add to RNO₂ [R = Ph, Ph₂CCH, Ph₂CC(Ph)] in the presence of t-BuHgI₂⁻ to form products derived from RN(OBu-t)O⁻HgI⁺.