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.     

Bipy,Phen und P(C6H4CH2NMe2‐2)3 in der Synthese kationischer Silber(I)‐Komplexe; die Festkörperstrukturen von [P(C6H4CH2NMe2‐2)3]AgOTf und [Ag(phen)2]OTf

Bipy, Phen, and P(C₆H₄CH₂NMe₂‐2)₃ in the Synthesis of Cationic Silver(I) Complexes; the Solid‐State Structures of [P(C₆H₄CH₂NMe₂‐2)₃]AgOTf and [Ag(phen)₂]OTf The reaction of [P(C₆H₄CH₂NMe₂‐2)₃]AgX ( 1a , X = OTf; 1b , X = OClO₃) with equimolar amounts of L^capL ( 2a , L^capL = 2, 2′‐bipyridine, bipy; 2b , L^capL = 4, 4′‐dimethyl‐2, 2′‐bipyridine, bipy′; 2c , L^capL = 1, 10‐phenanthroline, phen) leads to the formation of the cationic complexes {[P(C₆H₄CH₂NMe₂‐2)₃]Ag(L^capL)}⁺X^— (L^capL = bipy: 3a , X = OTf; 3b , X = ClO₄; L^capL = bipy′: 3c , X = OTf; 3d , X = ClO₄; L^capL = phen: 3e , X = OTf; 3f , X = ClO₄) in which the building blocks L^capL and P(C₆H₄CH₂NMe₂‐2)₃ act as bidentate chelating ligands and are datively‐bound to the silver atom. Spectroscopic studies reveal that on the NMR time‐scale the phosphane group is dynamic with exchanging the respective Me₂NCH₂ built‐in arms. While complex 3e is stable in the solid‐state, it appeared that solutions of 3e start to decompose upon precipitation of colloidal silver when they are heated or irradiated with light, respectively. Appropriate work‐up of the reaction mixture allows the isolation of the phosphane P(C₆H₄CH₂NMe₂‐2)₃ ( 5 ) along with [Ag(phen)₂]OTf ( 4 ). The solid‐state structures of neutral 1a and cationic 4 are reported. Mononuclear 1a crystallizes in the monoclinic space group P2₁/c with the cell parameters a = 16.7763(2), b = 14.7892(2), c = 25.44130(10)Å, β = 106.1260(10), V = 6063.83(11)ų and Z = 4 with 8132 observed unique reflections (R₁ = 0.0712), while 4 crystallizes in the monoclinic space group C2/c with the cell parameters a = 26.749(3), b = 7.1550(10), c = 26.077(3)Å, β = 113.503(2), V = 4576.8(10)ų and Z = 4 with 6209 observed unique reflections (R₁ = 0.0481). The unit cell of 1a consists of two independent molecules. In both molecules the silver atom possesses a distorted tetrahedral coordination sphere and a boat‐like conformation for the six‐membered AgPNCH₂C_2/phenyl cycles is found. In 4 , as typical for 1a , the silver atom possesses the coordination number 4. The two phen ligands are tilted by 40.63°. The OTf group is acting as non‐coordinating counter ion.     

Einkernige und zweikernige Kupfer(I)‐Komplexe vom Typ LCuCl,LCu2Cl2 und LCu2ClX [L = P(C6H4CH2NMe2)3; X = Br,I]

The title compounds 3‐5 are accessible by treatment of P(C₆H₄CH₂NMe2)₃( 1 ) with CuX ( 2a : X = Cl, 2b : X = Br, 2c : X = I) in the ratio of 1:1 or 1:2 in very good yields. Reaction of 1 with equimolar amounts of 2a affords the copper(I) chloride [P(C₆H₄CH₂NMe2)₃]CuCl ( 3 ). With a further equivalent of 2a homobimetallic [P(C₆H₄CH₂NMe2)₃]Cu₂Cl₂ ( 4 ) is formed, which also can be synthesized by the reaction of 1 with two equivalents of 2a. Complex 3 reacts with CuX (X = Br, I)to afford [P(C₆H₄CH₂NMe2)₃]Cu₂ClX ( 5a : X = Br; 5b : X = I) in which mixed halides are present. The newly synthesized complexes 3‐5 were characterized by elemental analyses, by their IR‐, ¹H‐, ¹³C{¹H}‐ and ³¹P{¹H}‐NMR spectra as well as by mass spectrometrical studies. The solid‐state structures of complexes 3 and 4 are reported. Mononuclear 3 crystallizes in the monoclinic space group P2₁/c with the cell parameters a = 14.285(2), b = 10.853(2), c = 17.425(2) Å , β = 103.310(10)?, V = 2628.9(7) Å ³ and Z = 4 with 4053 observed unique reflections; R₁ = 0.0314. The crystal structure of 3 consists of monomeric molecules with planar coordinated copper(I) centres (CuClNP). Homobimetallic 4 crystallizes in the monoclinic space group P2₁/n with a = 23.905(4), b = 10.874(3), c = 25.314(5), β = 99.130(10)?, V = 6497(2) /Aring; ³ and Z = 4 with 9021 observed unique reflections; R₁ = 0.0480. In 4 one of two copper(I) centres possesses a distorted trigonal‐pyramidal environment, while the other one is almost square‐pyramidal coordinated. The Cu₂Cl₂ segment resembles to a building block which is set up by a contact ion pair consisting of Cu⁺ and [CuCl₂]^‐ , respectively.     

Synthesis and Characterization of 1,3,2‐Bis (arylamino) phospholidine, 2‐oxide Derivatives: Crystal Structures of $\rm Cl(O)\overline{PN(p-Me-C_{6}H_{4})CH_{2}CH_{2}N}(p-Me-C_{6}H_{4})$ and $\rm ((CH_{2}C_{6}H_{5})(O)\overline{PN(p-Me-C_{6}H_{4})CH_{2}CH_{2}N}(p-Me-C_{6}H_{4})$

Using phosphoryl chloride as a substrate, a family of 1,3,2‐bis(arylamino) phospholidine, 2‐oxide of the general formula ; (X=Cl, 6a ; X=NMe₂, 1b ; X=N(CH₂C₆H₅)(CH₃), 2b ; X=NHC(O)C₆H₅, 3b ; X=4Me‐C₆H₄O, 4b ; X=C₆H₅O, 5b ; X=NHC₆H₁₁, 6b ; X=OC₄H₈N, 7b ; X=C₅H₁₀N, 8b ; X=NH₂, 9b ; X=F, 10b and Ar=4Me‐C₆H₄) was prepared and characterized by ¹H, ¹⁹F, ³¹P and ¹³C NMR and IR spectroscopy, and elemental analysis. A general and practical method for the synthesis of these compounds was selected. The structures of 6a and 2b were determined by single‐crystal X‐ray diffraction techniques. The low temperature NMR spectra of 2b revealed the restricted rotation of P‐N bond according to two independent molecules in crystalline lattice.     

Synthesis and characterization of novel chelated dimethylamino lithium alkoxides: molecular structures of [1‐LiOC(C6H11)2‐2‐NMe2C6H4]2 and [1‐LiOCPh2CH2‐2‐NMe2C6H4]2

From the reaction of 1‐HOCPh₂‐2‐NMe₂C₆H₄ ( 1 ), 1‐HOC(C₆H₁₁)₂‐2‐NMe₂C₆H₄ ( 2 ) and 1‐HOCPh₂CH₂‐2‐NMe₂C₆H₄ ( 3 ) with n‐BuLi in diethyl ether, the solvent‐free chelated dimethylamino lithium alkoxides [1‐LiOCPh₂‐2‐NMe₂C₆H₄]₂ ( 4 ), [1‐LiOC(C₆H₁₁)₂‐2‐NMe₂C₆H₄]₂ ( 5 ) and [1‐LiOCPh₂CH₂‐2‐NMe₂C₆H₄]₂ ( 6 ) were obtained. The lithium alkoxides 4 – 6 were characterized by ¹H, ⁷Li, and ¹³C NMR spectroscopy. Crystal structure determinations of 5 and 6 were carried out. Compounds 5 and 6 are examples of structurally characterized solvent‐free chelated dimethylamino lithium alkoxides and 6 is a rare example of this type containing a seven‐membered ring. Copyright © 2002 John Wiley & Sons, Ltd.     

1:1 Adducts of Copper(I) and Silver(I) Halides with the Olefinic Phosphane Tri(1‐cyclohepta‐2, 4, 6‐trienyl)phosphane. Molecular Structures of CuX[P(C7H7)3] (X = Cl,Br), AgCl[P(C7H7)3] and {Cu(μ3‐I)[P(C7H7)3]}4

A suspension of CuX (X = Cl, Br) or AgCl in organic solvents (such as CH₂Cl₂) reacts with P(C₇H₇)₃ ( 1 ) in a molar ratio 1:1 to give the mononuclear adducts CuX[P(C₇H₇)₃] (X = Cl ( 2a ), Br ( 2b )) and AgCl[P(C₇H₇)₃] ( 3a ) which crystallize as isotypic compounds in the orthorhombic space group Pnma (Z = 4). In the crystal, two (of the three) cyclohepta‐2, 4, 6‐trienyl substituents are present in the boat conformation, thus establishing a loose long‐distance interaction between the central double bond and the metal atom. A distorted pseudo‐tetrahedral coordination sphere is assumed to exist around the metal atom, with large P‐M‐X angles of 165.49(8)° ( 2a ), 162.07(7)° ( 2b ) and 168.54(3)° ( 3a ), respectively. The tetrameric 1:1 adduct {Cu(μ₃‐I)[P(C₇H₇)₃]}₄( 2c ) which was obtained from CuI and 1 in boiling ethanol, has also been characterized by X‐ray crystallography (monoclinic space group P2(1)/n, Z = 4); it contains all 12 cyclohepta‐2, 4, 6‐trienyl substituents in the chair conformation. The NMR spectra (¹H, ¹³C, ³¹P) of the new complexes 2a‐c and 3a indicate non‐rigid structures in solution. At room temperature, the ³¹P NMR signal of 3a appears as a doublet with an averaged coupling constant, ¹J(Ag, P), of 700.1 Hz, whereas at —45 °C the two expected doublets are clearly discernible with coupling constants ¹J(¹⁰⁷Ag, ³¹P) = 671.0 Hz and ¹J(¹⁰⁹Ag, ³¹P) = 774.4 Hz, respectively.     

Syntheses and Spectroscopic Study of Some New N‐4‐Fluorobenzoyl Phosphoric Triamides; Crystal Structures of 4‐F‐C6H4C(O)N(H)P(O)R2, R = NH‐C(CH3)3, NH‐CH2C6H5, N(CH3)(CH2C6H5)

Some new N‐4‐Fluorobenzoyl phosphoric triamides with formula 4‐F‐C₆H₄C(O)N(H)P(O)X₂, X = NH‐C(CH₃)₃ ( 1 ), NH‐CH₂‐CH=CH₂ ( 2 ), NH‐CH₂C₆H₅ ( 3 ), N(CH₃)(C₆H₅) ( 4 ), NH‐CH(CH₃)(C₆H₅) ( 5 ) were synthesized and characterized by ¹H, ¹³C, ³¹P NMR, IR and Mass spectroscopy and elemental analysis. The structures of compounds 1 , 3 and 4 were investigated by X‐ray crystallography. The P=O and C=O bonds in these compounds are anti. Compounds 1 and 3 form one dimensional polymeric chain produced by intra‐ and intermolecular ‐P=O···H‐N‐ hydrogen bonds. Compound 4 forms only a centrosymmetric dimer in the crystalline lattice via two equal ‐P=O···H‐N‐ hydrogen bonds. ¹H and ¹³C NMR spectra show two series of signals for the two amine groups in compound 1 . This is also observed for the two α‐methylbenzylamine groups in 5 due to the presence of chiral carbon atom in molecule. ¹³C NMR spectrum of compound 4 shows that ²J(P,C_aliphatic) coupling constant for CH₂ group is greater than for CH₃ in agreement with our previous study. Mass spectra of compounds 1 ‐ 3 (containing 4‐F‐C₆H₄C(O)N(H)P(O) moiety) indicate the fragments of amidophosphoric acid and 4‐F‐C₆H₄CN⁺ that formed in a pseudo McLafferty rearrangement pathway. Also, the fragments of aliphatic amines have high intensity in mass spectra.     

Synthese und Kristallstruktur des heterobimetallischen Diorganozinndichlorids (FcN,N)2SnCl2 (FcN,N—: (η5‐C5H5)Fe{(η5‐C5H3[CH(CH3)N(CH3)CH2CH2NMe2]‐2}—)

Synthesis and Crystal Structure of the Heterobimetallic Diorganotindichloride (FcN, N)₂SnCl₂ (FcN, N^—: (η⁵‐C₅H₅)Fe{η⁵‐C₅H₃[CH(CH₃)N(CH₃)CH₂CH₂NMe₂]‐2}^—) The heterobimetallic title compound [(FcN, N)₂SnCl₂] ( 1 ) was obtained by the reaction of [LiFcN, N] with SnCl₄ in the molar ratio 1:1 in diethylether as a solvent. The two FcN, N^— ligands in 1 are bound to Sn through a C‐Sn σ‐bond; the amino N atoms of the side‐chain in FcN, N^— remain uncoordinated. The crystals contain monomeric molecules with a pseudo‐tetrahedral coordination at the Sn atom: Space group P2₁/c; Z = 4, lattice dimensions at —90 °C: a = 9.6425(2), b = 21.7974(6), c = 18.4365(4) Å, β = 100.809(2)°, R1_obs· = 0.051, wR2_obs· = 0.136.     

Weak Interionic Interactions in 2‐Haloimidazolium Hexahalotellurates(IV) [1]

The 2‐haloimidazolium salts [C₁₁H₂₀N₂X]X [ 1 ; X = Cl ( a ), Br ( b )] react with TeX₄ to give the salts [C₁₁H₂₀N₂X]₂[TeX₆] [ 2 ; X = Cl ( a ), Br ( b )]. The crystal structure analyses of 2a and 2b · CH₂Cl₂ reveal the presence of ionic pairs linked by weak halogen to halogen interactions.     

Hypervalent selenium compounds containing N → Se intramolecular interactions: synthesis,characterization and X‐ray structures of [2‐(Me2NCH2)C6H4]SeS(S)PR2 (R = Ph,OiPr)

[2‐(Me₂NCH₂)C₆H₄]Se? S(S)PR₂ [R = Ph (1), OⁱPr (2)] were prepared by reacting [2‐(Me₂NCH₂)C₆H₄]₂Se₂ with the appropriate disulfanes, [R₂P(S)S]₂. The compounds were characterized by multinuclear magnetic resonance (¹H, ¹³C, ³¹P). The molecular structures of 1 and 2 were determined by single‐crystal X‐ray diffraction. Both compounds are monomeric and the nitrogen atom of the pendent CH₂NMe₂ arm is strongly coordinated to the selenium atom. The organophosphorus ligands are monodentate, thus resulting in a T‐shaped coordination geometry around selenium. Copyright © 2002 John Wiley & Sons, Ltd.     

[2+4] and [2+2] Cycloaddition Reactions of N‐Sulfinyl Carboxylic Acid Amides with (CF3)2BNMe2. Crystal Structure of cyclo‐(CF3)2B‐NMe2‐S(=O)‐N=C(p‐CH3C6H4)‐O

N‐sulfinylacylamides R‐C(=O)‐N=S=O react with (CF₃)₂BNMe₂ ( 1 ) to form, by [2+4] cycloaddition, six‐membered rings cyclo‐(CF₃)₂B‐NMe₂‐S(=O)‐N=C(R)‐O for R = Me ( 2 ), t‐Bu ( 3 ), C₆H₅ ( 4 ), and p‐CH₃C₆H₄ ( 5 ) while N‐sulfinylcarbamic acid esters R‐O‐C(=O)‐N=S=O react with 1 to yield mixtures of six‐membered (cyclo‐(CF₃)₂B‐NMe₂‐S(=O)‐N=C(OR)‐O) and four‐membered rings (cyclo‐(CF₃)₂B‐NMe₂‐S(=O)‐N(C=O)OR) for R = Me ( 6 and 9 ), Et ( 7 and 10 ), and C₆H₅ ( 8 and 11 ). The structure of 5 has been determined by X‐ray diffraction.     

Phosphonium Salts of 1,8‐Bis(diphenylphosphino)naphthalene: Molecular Structures and NMR‐spectroscopic Studies

A representative series of diphosphine monophosphonium salts [1‐Ph₂P(C₁₀H₆)‐8‐PRPh₂]⁺X^– ( 2 b : R = H, X = CF₃SO₃; 4 : R = Me, X = CF₃SO₃; 5 : R = C₆H₅CH₂ = Bn, X = Br) has been prepared by treatment of 1,8‐bis(diphenylphosphino)naphthalene (dppn, 1 ) with stoichiometric amounts of HSO₃CF₃ or CH₃SO₃CF₃ in CH₂Cl₂ at +20 °C and with C₆H₅CH₂Br in toluene at +80 °C. Their X‐ray crystal structures show that there is no evidence for dative P → P⁺ interactions. Instead, steric repulsion deflects the substituent groups to opposite faces of the naphthalene plane [splay angles: +11.4° ( 2 b ), +13.6° ( 4 ); +16.7° ( 5 )]. In solution 2 b , 4 , and 5 were dynamic according to ³¹P, ¹³C, and ¹H NMR spectroscopy. The fluxionality of 2 b involves rapid intramolecular proton exchange between the two phosphorus atoms, which slows down at low temperature, whereas the dynamic behaviour of 4 and 5 is interpreted in terms of hindered rotation of the bulky RPh₂P⁺ groups (R = Me or Bn) about the P–C(naphthyl) bond. Treatment of 1,8‐bis(diphenylphosphoryl)naphthalene (dppnO₂, 6 ) with HSO₃CF₃ gave the protonated bis(phosphine oxide), as the triflate salt, dppnO₂H⁺ CF₃SO₃^– ( 7 ). The X‐ray structure analysis of 7 revealed a highly strained molecule (P1…P2 365.5 pm) in which the P=O bonds point to the same face of the naphthalene plane to accommodate the proton. All isolated compounds were characterised by a combination of ³¹P, ¹H, and ¹³C NMR spectroscopy, IR spectroscopy ( 7 ), mass spectrometry and elemental analysis.     

1‐Azonia‐2‐boratanaphthalenes

The 1‐azonia‐2‐boratanaphthalenes (NH)(BX)C₈H₆ can be synthesized from 2‐aminostyrene and the dihaloboranes XBHal₂ ( 1 ‐ 4 : X = Cl, Br, iPr, tBu). Further derivatives (NH)(BX)C₈H₆ are obtained from 1 by replacing Cl by alkoxy or alkyl groups [ 5 ‐ 8 : X = OMe, OtBu, Me, (CH₂)₃NMe₂]. The hydrolysis of 1 gives a mixture of the bis(azoniaboratanaphthyl) oxide [(NH)BC₈H₆]₂O ( 9 ) and the hydroxy derivative (NH)[B(OH)]C₈H₆ ( 10 ). The diboryl oxide 9 crystallizes in the space group C2/c. The lithiation of 4 at the nitrogen atom gives [NLi(tmen)](BtBu)C₈H₆ ( 11 ), which upon reaction with the diborane(4) B₂Cl₂(NMe₂)₂ yields the 1, 2‐bis(azoniaboratanaphthyl)diborane B₂[N(BtBu)C₈H₆]₂(NMe₂)₂ ( 12 ). The 2‐chloro‐1‐methyl‐4‐phenyl derivative (NMe)(BCl)C₈H₅Ph ( 13 ) of the parent (NH)(BH)C₈H₆ can be synthesized from the aminoborane BCl₂(NMePh) and phenylethyne. Substitution of Cl in 13 gives the derivatives (NMe)(BX)C₈H₅Ph [ 14 ‐ 20 : X = N(SiMe₃)₂, Me, Et, iBu, tBu, CH₂SiMe₃, Ph] and the reaction of 13 with Li₂O affords the bis(azoniaboratanaphthyl) oxide [(NMe)BC₈H₅Ph]₂O ( 21 ). The reaction of 16 or 19 with [(MeCN)₃Cr(CO)₃] yields the complexes [{(NMe)(BX)C₈H₅Ph}Cr(CO)₃] ( 22 , 23 : X = Et, CH₂SiMe₃), in which the chromium atom is hexahapto bound to the homoarene part of 16 or 19 , respectively. The complex 23 crystallizes in the space group P2₁/c. Upon reaction of the phenols para‐C₆H₄R(OH) with the aryldichloroboranes ArBCl₂ and subsequent condensation of the products with phenylethyne, the 1‐oxonia‐2‐boratanaphthalenes O(BAr)C₈H₄RPh with R in position 6 and Ph in position 4 are formed ( 24 ‐ 26 : Ar = Ph, R = H, Me, OMe; 27 ‐ 29 : Ar = C₆F₅, R = H, Me, OMe). The azoniaboratanaphthalenes 1 ‐ 23 were characterized by NMR methods.     

Four‐ and Five‐Coordinate Gallium Complexes Stabilized by Bidentate 2‐(Dimethylaminomethyl)Pyrrole Ligand: Molecular Structures of Ga[NC4H3(CH2NMe2)‐2]3 and GaMe2[NC4H3(CH2NMe2)‐2]

Treatment of GaCl₃ with one equiv of Li[NC₄H₃(CH₂NMe₂)‐2] (n = 1, 2, 3) in diethyl ether at ?78 °C yields GaCl_3‐n[NC₄H₃(CH₂NMe₂)‐2]_n (n = 1, 1 ; n = 2, 2 ; n = 3, 3 ). Compound 1 reacts with two equiv of RLi to afford GaR₂[NC₄H₃(CH₂NMe₂)‐2] ( 4a, R=Me; 4b, R=Bu ) via transmetallation. Reacting 2 with one equiv of RLi in diethyl ether, 3 and 4 are formed via ligand redistribution. Variable temperature ¹H NMR spectroscopic experiments reveal that the five‐coordinate gallium compound 3 is fluxional and results in a coalescence temperature at 5 °C, at which ΔG^≠ is calculated at ca. 10.4 Kcal/mole. All the new compounds have been characterized by ¹H and ¹³C NMR spectroscopy and the structures of compounds 3 and 4a have also been determined by X‐ray crystallography.     

Fluoroborates by Cleavage of Trimethylamine‐bis(trifluoromethyl)boranes with NEt3 × 3 HF. Structures of C6F5(CF3)2B · NMe3, K[C6H5CH2(CF3)2BF], and K[C6H5(CF3)2BF]

Trimethylamine‐bis(trifluoromethyl)boranes R(CF₃)₂B · NMe₃ (R = cis/trans‐CF₃CF=CF ( 1/2 ), HC≡C ( 3 ), H₂C=CH ( 4 ), C₂H₅ ( 5 ), C₆H₅CH₂ ( 6 ), C₆F₅ ( 7 ), C₆H₅ ( 8 )) react with NEt₃ × 3 HF depending on the nature of R at 155–200 °C under replacement of the trimethylamine ligand to form the corresponding fluoro‐bis(trifluoromethyl)borates [R(CF₃)₂BF]^– ( 1 a/2 a – 8 a ). The structures of 7 , K[C₆H₅CH₂(CF₃)₂BF] ( K‐6 a ), and K[C₆H₅(CF₃)₂BF] ( K‐8 a ) have been investigated by single‐crystal X‐ray diffraction. In 7 the CF₃ groups make short repulsive contacts with NMe₃ and C₆F₅ entities – the B–CF₃ bonds being unusually long. The B–F bond lengths of K‐6 a and K‐8 a (1.446(3) and 1.452(2) Å, respectively) are long for a fluoroborate.     

Structure and Bonding in Bis(1‐naphthyl) Diselenide and Bis{[2‐(N,N‐dimethylamino)methyl]phenyl} Tetraselenide,and Their Brominated Derivatives

The formation and crystal structures of bis(1‐naphthyl) diselenide ( 1 ) and bis{[2‐(N,N‐dimethylamino)methyl]phenyl} tetraselenide ( 2 ) are described. Whereas 1 can be produced in good yields, 2 is formed only as a minor product together with the known main product, bis{[2‐(N,N‐dimethylamino)methyl]phenyl} diselenide. The composition of the reaction mixture is semi‐quantitatively estimated by ⁷⁷Se NMR spectroscopy and DFT calculations. The effect of the n²→σ*(Se–Se) and π→σ*(Se–Se) secondary bonding interactions on the Se–Se bonds is discussed both by DFT calculations and comparison with literature, as available. The bromination of 1 yields monomeric (1‐naphthyl)selenenyl bromide ( 3 ) in good yields. That of the reaction mixture of (C₆H₄CH₂NMe₂)Se_x (x = 2–4) and Se₈ afforded (C₆H₄CH₂NMe₂H)₂[SeBr₄] ( 4 ) and (C₆H₄CH₂NMe₂H)₂[SeBr₆] ( 5 ) in addition to (C₆H₄CH₂NMe₂)SeBr, which has been previously reported.     

Novel structures of cyclometallated complexes of palladium(II) derived from terdentate ligands. Crystal and molecular structure of [Pd{C6H4C(H)=NCH2CH2CH2NMe2}(X)] (X=Cl, Br, I)

Treatment of N-(2-chlorobenzylidene)-N,N-dimethyl-1,3-propanediamine (1) and N-(2-bromo-3,4-(MeO)₂-benzylidene)-N,N-dimethyl-1,3-propanediamine (20) with tris(dibenzylideneacetone)dipalladium(0) in toluene gave the mononuclear cyclometallated complexes [Pd{C₆H₄C(H)=NCH₂CH₂CH₂NMe₂}(Cl)] (2) and [Pd{3,4-(MeO)₂C₆H₂C(H)=NCH₂CH₂CH₂NMe₂}(Br)] (21), respectively, via oxidative addition reaction with the ligand as a C,N,N terdentate ligand. Reaction of 2 with sodium bromide or iodide in an acetone–water mixture gave the cyclometallated analogues of 2, [Pd{C₆H₄C(H)=NCH₂CH₂CH₂NMe₂}(Br)] (3) and [Pd{C₆H₄C(H)=NCH₂CH₂CH₂NMe₂}(I)] (4), by halogen exchange. The X-ray crystal structures of 2, 3 and 4 were determined and discussed. Treatment of 2, 3, 4 and 21 with tertiary monophosphines in acetone gave the mononuclear cyclometallated complexes [Pd{C₆H₄C(H)=NCH₂CH₂CH₂NMe₂}(L)(X)] (6: L=PPh₃, X=Cl; 7: L=PPh₃, X=Br; 8: L=PPh₃, X=I; 9: L=PMePh₂, X=Cl; 10: L=PMe₂Ph, X=Cl) and [Pd{3,4-(MeO)₂C₆H₂C(H)=NCH₂CH₂CH₂NMe₂}(L)(Br)] (22: L=PPh₃; 23: L=PMePh₂; 24: L=PMe₂Ph). A fluxional behaviour due to an uncoordinated CH₂CH₂CH₂NMe₂ could be determined by variable temperature NMR spectroscopy. Treatment of 2, 3 and 4 with silver trifluoromethanesulfonate followed by reaction with triphenylphosphine gave the mononuclear complex [Pd{C₆H₄C(H)=NCH₂CH₂CH₂NMe₂}(PPh₃)][F₃CSO₃] (11) where the Pd–NMe₂ bond was retained. Reaction of 2, 3 and 4 with ditertiary diphosphines in a cyclometallated complex–diphosphine 2:1 molar ratio gave the binuclear complexes [{Pd[C₆H₄C(H)=NCH₂CH₂CH₂NMe₂](X)}₂(μ-L–L)][L–L=PPh₂(CH₂)₄PPh₂(dppb) (13, X=Cl; 14, X=Br; 15, X=I; L–L=PPh₂(CH₂)₅PPh₂(dpppe): 16, X=Cl; 17, X=Br; 18, X=I) with palladium–NMe₂ bond cleavage. Treatment of 2, 3 and 4 with ditertiary diphosphines, in a cyclometallated complex–diphosphine 2:1, molar ratio and AgSO₃CF₃ gave the binuclear cyclometallated complexes [{Pd[C₆H₄C(H)=NCH₂CH₂CH₂NMe₂]}₂(μ-L–L)][F₃CSO₃]₂ (11: L–L=PPh₂(CH₂)₄PPh₂(dppb), X=Cl; 12: L–L=PPh₂(CH₂)₅PPh₂ (dpppe), X=Cl). Reaction of 2 with the ditertiary diphosphine cis-dppe in a cyclometallated complex–diphosphine 1:1 molar ratio followed by treatment with sodium perchlorate gave the mononuclear cyclometallated complex [Pd{C₆H₄C(H)=NCH₂CH₂CH₂NMe₂}(cis-PPh₂CH=CHPPh₂–P,P)][ClO₄] (19).     

Differing Coordination Modes of (O‐Alkyl)‐p‐Ethoxyphenyldithiophosphonato Ligands in Copper(I), Silver(I) and Gold(I) Triphenylphosphine Complexes

The three (O‐methyl)‐p‐ethoxyphenyldithiophosphonato triphenylphosphine complexes of copper, silver and gold, [(Ph₃P)_nM{S₂P(OMe)C₆H₄OEt‐p}] (M = Cu, n = 2; M = Ag, Au, n = 1) investigated structurally by X‐ray diffraction exhibit remarkable structural differences. The copper compound is a four‐coordinate chelate monomer with Cu–S 2.4417(6) and 2.5048(6) Å; P–Cu–S 104.24(2)–114.01(2)°; Cu–S–P 82.49(3)° and 80.85(2)°. The silver compound is a cyclic dimer with bridging dithiophosphonato ligands and three‐coordinate silver atoms [Ag–S 2.5371(5) and 2.6867(5) Å; P–Ag–S 122.88(2)° and 122.17(2)°; Ag–S–P 89.32(2)° and 103.56(2)°]. The gold compound is monomeric with linear dicoordinate gold [Au–S 2.3218(6) Å; P–Au–S 177.72(2)°, Au–S–P 100.97(3)°].     

The seven‐membered nickelacycle [NiBr{o‐CH=C(CF3)C6H4CH2PPh2‐κ2C,P}{PPh(CH2Ph)2}]

The crystal and molecular structures of the title compound, 3‐bromo‐3‐(di­benzyl­phenyl­phospho­nio)‐2,2‐di­phenyl‐5‐trifluoromethyl‐1H‐benzo­[e][1,2]­phosphanickelepine, [NiBr(C₂₂H₁₇F₃P)(C₂₀H₁₉P)], which was obtained as the major regioisomer from insertion of HCCCF₃ into the Ni—C bond of the five‐membered phosphanickelacycle [NiBr(o‐C₆H₄CH₂PPh₂‐κ²C,P){PPh(CH₂Ph)₂}], have been determined. Principal geometric data include the Ni—X bond lengths Ni—Br 2.3343 (4) Å, Ni—P 2.1867 (7) and 2.2094 (7) Å, and Ni—C 1.882 (3) Å, and the two trans angles P—Ni—P 171.55 (3)° and Br—Ni—C 176.88 (9)°.     

Platinum(II) and Palladium(II) Halides and Pseudohalides with the Ligand Tri(1‐cyclohepta‐2, 4, 6‐trienyl)phosphane. X‐Ray Structural Analysis of [P(C7H7)2(η2‐C7H7)]PtI2

Tri(1‐cyclohepta‐2, 4, 6‐trienyl)phosphane, P(C₇H₇)₃ ( 1 ) ([P] when coordinated to a metal) stabilizes platinum(II) ( 2 ) and palladium(II) dihalides ( 3 ) as [P]MX₂ with X = Cl ( a ), Br ( b ) and I ( c ). The phosphane coordinates to the metal as a chelate ligand via both phosphorus and the central η²‐C=C bond of one of the cyclohepta‐2, 4, 6‐trienyl rings. The complexes were prepared by various routes, mainly by the reaction of (cod)MCl₂ (cod = cycloocta‐1, 5‐diene) with 1 to give the chlorides 2a and 3a , which then could be converted into the bromides 2b , 3b or the iodides 2c , 3c by reaction with NaBr or NaI, respectively. The molecular structure of 2c was determined by X‐ray analysis. Treatment of 2a and 3a with sodium or potassium salts of several pseudohalides afforded the complexes [P]MX₂ 2d (NCO/NCO), 2e₁ (NCS/SCN), 2e₁' (SCN/NCS), 2f₂ (SeCN/SeCN), 3f₁ (NCSe/SeCN), 2g and 3g (X = N₃). Attempts failed to synthesize the cyanides 2h and 3h by the same route. By using an excess of trimethylsilyl cyanide in the reaction with 2a in THF solution, the complex trans‐{[(C₇H₇)₃P]₂Pt(CN)₂} ( 4h ) was obtained instead of 2h . The analogous complexes trans‐{[(C₇H₇)₃P]₂MX₂} with M = Pt ( 4 ) and Pd ( 5 ) for X = Cl ( a ), Br ( b ), I ( c ) could be prepared from the reaction of the corresponding tetrahalogenometallates and 1 (in the case of 5c from PdI₂ and 1 ). In contrast to 4h , the complexes 4a‐c and 5a‐c were found to be labile in solution with respect to partial loss of the phosphane 1 and rearrangement into 2a‐c and 3a‐c , respectively. All compounds were characterized by IR spectroscopy and by multinuclear magnetic resonance spectroscopy (¹H, ¹³C, ³¹P, ⁷⁷Se and ¹⁹⁵Pt NMR). The ligand [P] in 2 and 3 is fluxional with regard to coordination of the C₇H₇ rings to the metal.