Strukturen von Bis(trifluormethyl)halogeno‐ und ‐thiocyanato‐mercuraten, [Hg(CF3)2X]— (X = Br,I, SCN), und ein Vergleich der Strukturparameter der CF3‐Gruppen

Structures of Bis(trifluoromethyl)halogeno and thiocyanato Mercurates, [Hg(CF₃)₂X]^— (X = Br, I, SCN), and a Comparison of the Structural Parameters of the CF₃ Groups [(18‐C‐6)K]₂[Hg(CF₃)₂SCN]₂ (1) and [P(CH₃)(C₆H₅)₃]₂[Hg(CF₃)₂X]₂ (X = Br (2) , I (3) ) are prepared and their crystal structures are determined. [(18‐C‐6)K]₂[Hg(CF₃)₂SCN]₂ (1) crystallizes in the monoclinic space group P2₁/c with Z = 2, [P(CH₃)(C₆H₅)₃]₂[Hg(CF₃)₂Br]₂ (2) in the monoclinic space group P2₁/n with Z = 2 and [P(CH₃)(C₆H₅)₃]₂[Hg(CF₃)₂I]₂ (3) in the triclinic space group P1¯ with Z = 1. In the solid state the three compounds form dimeric anions with planar Hg₂X₂ rings. The structural parameters of the Hg(CF₃)₂ units in the till now known bis(trifluoromethyl)halogeno mercurates are compared. In all compounds one nearly symmetric and one distorted CF₃ group exist. The largest differences of the C—F bond lengths is found for [(18‐C‐6)K][Hg(CF₃)₂I]. This can be regarded as the experimental evidence for the properties of trifluoromethyl mercury compounds to act as excellent difluorocarbene sources in the presence of alkali iodides.     

Syntheses of Trifluoromethanethiolato Platinum(II) Complexes – Crystal Structures of cis‐Pt(SCF3)2(PPh3)2 and trans‐Pt(SCF3)Cl(PPh3)2

Ligand exchange reactions of cis‐PtCl₂(PPh₃)₂ and [NMe₄]SCF₃ in different ratios were studied. Depending on the stoichiometry reactions proceeded with formation of products expected for the chosen ratio, i. e. cis‐Pt(SCF₃)Cl(PPh₃)₂, cis‐Pt(SCF₃)₂(PPh₃)₂, and [NMe₄][Pt(SCF₃)₃(PPh₃)]. Starting from cis‐PtCl₂(MeCN)₂ and [NMe₄]SCF₃ and adding PPh₃ after substitution, product mixtures were dominated by the corresponding trans‐isomers. Results of the single crystal structure analyses of cis‐Pt(SCF₃)₂(PPh₃)₂ and trans‐Pt(SCF₃)Cl(PPh₃)₂ are discussed.     

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)°.     

Synthesen und Kristallstrukturen von [Pd9As8(PPh3)8] und [Pd9Sb6(PPh3)8]

Syntheses and Crystal Structures of [Pd₉As₈(PPh₂)₈] and [Pd₉Sb₆(PPh₃)₈] [PdCl₂(PPh₃)₂] reacts with As(SiMe₃)₃ to give the new cluster [Pd₉As₈(PPh₃)₈] ( 4 ). 4 has been characterized by X-ray crystal structure analysis. It is a molecule in which four [Pd₂(PPh₃)₂]-units are bridged by As₂-units. A further Pd atom is located in the centre of the cluster. 4 crystallizes in the space group C2/c with four formula units per unit cell. The lattice constants at 200 K are: a = 3 970.6(3), b = 1 648.90(16), c = 3 266.30(20) pm, β = 131,44(4)°. The reaction of [PdCl₂(PPh₃)₂] with Sb(SiMe₃)₃ yields [Pd₉Sb₆(PPh₃)₈] ( 5 ). 5 consists of a body centred cubic Pd₉-cluster. All of the cube faces are capped by μ₄-Sb-ligands. 5 crystallizes in the space group Pn3 with two formula units per unit cell. The lattice constants at 200 K are: a = b = c = 1 995.4(2) pm.     

Synthesen und NMR‐Untersuchungen von Salzen mit den neuen Anionen [PtXn(CF3)6‐n]2— (n = 0 ‐ 5, X = F,OH, Cl,CN) und die Kristallstrukturanalyse von K2[(CF3)2F2Pt(μ‐OH)2PtF2(CF3)2]·2H2O

Syntheses and NMR Spectroscopic Ivestigations of Salts containing the Novel Anions [PtX_n(CF₃)_6‐n]^2— (n = 0 ‐ 5, X = F, OH, Cl, CN) and Crystal Structure of K₂[(CF₃)₂F₂Pt(μ‐OH)₂PtF₂(CF₃)₂]·2H₂O The first syntheses of trifluoromethyl‐complexes of platinum through fluorination of cyanoplatinates are reported. The fluorination of tetracyanoplatinates(II), K₂[Pt(CN)₄], and hexacyanoplatinates(IV), K₂[Pt(CN)₆], with ClF in anhydrous HF leads after working up of the products to K₂[(CF₃)₂F₂Pt(μ‐OH)₂PtF₂(CF₃)₂]·2H₂O. The structure of the salt is determined by a X‐ray structure analysis, P2₁/c (Nr. 14), a = 11.391(2), b = 11.565(2), c = 13.391(3)Å, β = 90.32(3)°, Z = 4, R₁ = 0.0326 (I > 2σ(I)). The reaction of [Bu₄N]₂[Pt(CN)₄] with ClF in CH₂Cl₂ generates mainly cis‐[Bu₄N]₂[PtCl₂(CF₃)₄] and fac‐[Bu₄N]₂[PtCl₃(CF₃)₃], but in contrast that of [Bu₄N]₂[Pt(CN)₆] with ClF in CH₂Cl₂ results cis‐[Bu₄N]₂[PtX₂(CF₃)₄], [Bu₄N]₂[PtX(CF₃)₅] (X = F, Cl) and [Bu₄N]₂[Pt(CF₃)₆]. In the products [Bu₄N]₂[PtX_n(CF₃)_6‐n] (X = F, Cl, n = 0—3) it is possibel to exchange the fluoro‐ligands into chloro‐ and cyano‐ligands by treatment with (CH₃)₃SiCl und (CH₃)₃SiCN at 50 °C. With continuing warming the trifluoromethyl‐ligands are exchanged by chloro‐ and cyano‐ligands, while as intermediates CF₂Cl and CF₂CN ligands are formed. The identity of the new trifluoromethyl‐platinates is proved by ¹⁹⁵Pt‐ and ¹⁹F‐NMR‐spectroscopy.     

One‐dimensionally linked Chain Crown Ether Complexes. Syntheses and Crystal Structures of Complexes [K(18‐Crown‐6)]2[M(SeCN)4](H2O) (M = Pd,Pt)

18‐crown‐6(18‐C‐6) complexes with K₂[M(SeCN)₄] (M = Pd, Pt): [K(18‐C‐6)]₂[Pd(SeCN)₄] (H₂O) ( 1 ) and [K(18‐C‐6)]₂[Pt(SeCN)₄](H₂O) ( 2 ) have been isolated and characterized by elemental analysis, IR spectroscopy and single crystal X‐ray analysis. The complexes crystallize in the monoclinic space group P2₁/n with cell dimensions: 1 : a = 1.1159(3) Å, b = 1.2397(3) Å, c = 1.6003(4) Å, β = 92.798(4)°, V = 2.2111(8) ų, Z = 2, F(000) = 1140, R₁ = 0.0418, wR₂ = 0.0932 and 2 : a = 1.1167(3) Å, b = 1.2394(3) Å, c = 1.5968(4) Å, β = 92.945(4)°, V = 2.2071(9) ų, Z = 2, F(000) = 1204, R₁ = 0.0341, wR₂ = 0.0745. Both complexes form one‐dimensionally linked chains of [K(18‐C‐6)]⁺ cations and [M(SeCN)₄]^2— (M = Pd, Pt) anions bridged by K‐O‐K interactions between adjacent [K(18‐C‐6)]⁺ units.     

Kristallstrukturen,spektroskopische Charakterisierung und Normalkoordinatenanalyse von (n‐Bu4N)2[M(ECN)4] (M = Pd,Pt; E = S,Se)

Crystal Structures, Spectroscopic Analysis, and Normal Coordinate Analysis of ( n ‐Bu₄N)₂[M(ECN)₄] (M = Pd, Pt; E = S, Se) The reaction of (NH₄)₂[PdCl₄] or K₂[PtCl₄] with KSCN or KSeCN in aqueous solutions yields the complex anions [Pd(SCN)₄]^2–, [Pt(SCN)₄]^2– and [Pt(SeCN)₄]^2–, which are converted into (n‐Bu₄N) salts with (n‐Bu₄N)HSO₄. (n‐Bu₄N)₂[Pd(SeCN)₄] is formed by treatment of (n‐Bu₄N)₂[PdCl₄] with (n‐Bu₄N)SeCN in acetone. X‐ray structure determinations on single crystals of (n‐Bu₄N)₂[Pd(SCN)₄] (monoclinic, space group P2₁/n, a = 13.088(3), b = 12.481(2), c = 13.574(3) Å, β = 91.494(15)°, Z = 2), (n‐Bu₄N)₂[Pd(SeCN)₄] (monoclinic, space group P2₁/n, a = 13.171(2), b = 12.644(2), c = 13.560(2) Å, β = 91.430(11)°, Z = 2) and (n‐Bu₄N)₂[Pt(SeCN)₄] (monoclinic, space group P2₁/n, a = 13.167(2), b = 12.641(1), c = 13.563(2) Å, β = 91.516(18)°, Z = 2) reveal, that the compounds crystallize isotypically and the complex anions are centrosymmetric and approximate planar. In the Raman spectra the metal ligand stretching modes of (n‐Bu₄N)₂[Pd(SCN)₄] ( 1 ) and (n‐Bu₄N)₂[Pt(SCN)₄] ( 3 ) are observed in the range of 260–303 cm^–1 and of (n‐Bu₄N)₂[Pd(SeCN)₄] ( 2 ) and (n‐Bu₄N)₂[Pt(SeCN)₄] ( 4 ) in the range of 171–195 cm^–1. The IR and Raman spectra are assigned by normal coordinate analysis using the molecular parameters of the X‐ray determination. The valence force constants are f_d(PdS) = 1.17, f_d(PdSe) = 1.17, f_d(PtS) = 1.44 and f_d(PtSe) = 1.42 mdyn/Å. The ⁷⁷Se NMR resonances are 23 for 2 , –3 for 4 and the ¹⁹⁵Pt NMR resonances 549 for 3 and 130 ppm for 4 .     

[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.     

Eine neue Form von PdSCl: Der molekulare Komplex Tris(μ4‐disulfido)‐hexa‐μ2‐chloro‐hexapalladium(II) [Pd6(S2)3Cl6]

The Molecular Complex Tris(μ₄‐disulfido)‐hexa‐μ₂‐chloro‐hexapalladium [Pd₆(S₂)₃Cl₆] A new hexameric form of PdSCl have been obtained by reaction of Pd metal with sulfur in SCl₂ solution at 180 °C in a closed silica ampoule. The monoclinic crystal structure of β‐PdSCl (space group P2₁ /m; a = 7.766(2)Å; b = 11.941(2)Å; c = 9.136(3)Å; β = 110.57(3)°; Z =12) is built up by clusters [Pd₆(S₂)₃Cl₆] with nearly D_3h symmetry. In the molecular units six Pd atoms form a trigonal prism with three S₂ disulfide groups in front of the side faces. The fourfold coordination of the Pd atoms is completed by 6 Cl atoms forming μ₂ bridges.     

Darstellung,Kristallstrukturen und Schwingungsspektren von [Pt(N3)6]2– und [Pt(N3)Cl5]2–, 195Pt‐ und 15N‐NMR‐Spektren von [Pt(N3)nCl6–n]2– und [Pt(15NN2)n(N215N)6–n]2–, n = 0–6

Synthesis, Crystal Structures, and Vibrational Spectra of [Pt(N₃)₆]^2– and [Pt(N₃)Cl₅]^2–, ¹⁹⁵Pt and ¹⁵N NMR Spectra of [Pt(N₃)_nCl_6–n]^2– and [Pt(¹⁵NN₂)_n(N₂¹⁵N)_6–n]^2–, n = 0–6 By ligand exchange of [PtCl₆]^2– with sodium azide mixed complexes of the series [Pt(N₃)_nCl_6–n]^2– and with ¹⁵N‐labelled sodium azide (Na¹⁵NN₂) mixtures of the isotopomeres [Pt(¹⁵NN₂)_n(N₂¹⁵N)_6–n]^2–, n = 0–6 and the pair [Pt(¹⁵NN₂)Cl₅]^2–/[Pt(N₂¹⁵N)Cl₅]^2– are formed. X‐ray structure determinations on single crystals of (Ph₄P)₂[Pt(N₃)₆] ( 1 ) (triclinic, space group P1, a = 10.175(1), b = 10.516(1), c = 12.380(2) Å, α = 87.822(9), β = 73.822(9), γ = 67.987(8)°, Z = 1) and (Ph₄As)₂[Pt(N₃)Cl₅] · HCON(CH₃)₂ ( 2 ) (triclinic, space group P1, a = 10.068(2), b = 11.001(2), c = 23.658(5) Å, α = 101.196(14), β = 93.977(15), γ = 101.484(13)°, Z = 2) have been performed. The bond lengths are Pt–N = 2.088 ( 1 ), 2.105 ( 2 ) and Pt–Cl = 2.318 Å ( 2 ). The approximate linear azido ligands with N^α–N^β–N^γ‐angles = 173.5–174.6° are bonded with Pt–N^α–N^β‐angles = 116.4–121.0°. In the vibrational spectra the PtCl stretching vibrations of (n‐Bu₄N)₂[Pt(N₃)Cl₅] are observed at 318–345, the PtN stretching modes of (n‐Bu₄N)₂[Pt(N₃)₆] at 401–428 and of (n‐Bu₄N)₂[Pt(N₃)Cl₅] at 408–413 cm^–1. The mixtures (n‐Bu₄N)₂[Pt(¹⁵NN₂)_n(N₂¹⁵N)_6–n], n = 0–6 and (n‐Bu₄N)₂[Pt(¹⁵NN₂)Cl₅]/(n‐Bu₄N)₂[Pt(N₂¹⁵N)Cl₅] exhibit ¹⁵N‐isotopic shifts up to 20 cm^–1. Based on the molecular parameters of the X‐ray determinations the vibrational spectra are assigned by normal coordinate analysis. The average valence force constants are f_d(PtCl) = 1.93, f_d(PtN^α) = 2.38 and f_d(N^αN^β, N^βN^γ) = 12.39 mdyn/Å. In the ¹⁹⁵Pt NMR spectrum of [Pt(N₃)_nCl_6–n]^2–, n = 0–6 downfield shifts with the increasing number of azido ligands are observed in the range 4766–5067 ppm. The ¹⁵N NMR spectrum of (n‐Bu₄N)₂[Pt(¹⁵NN₂)_n(N₂¹⁵N)_6–n], n = 0–6 exhibits by ¹⁵N–¹⁹⁵Pt coupling a pseudotriplett at –307.5 ppm. Due to the isotopomeres n = 0–5 for terminal ¹⁵N six well‐resolved signals with distances of 0.03 ppm are observed in the low field region at –201 to –199 ppm.     

Molekülstruktur und thermische Stabilität des metallacyclischen Platin(II)‐Komplexes [Li(TMEDA)]2Pt(CH2CMe2CMe2CH2)2

Molecular Structure and Thermal Stability of the Metallacyclic Platinum(II) Complex [Li(TMEDA)]₂Pt(CH₂CMe₂CMe₂CH₂)₂ The X‐ray investigation at the “ate‐complex” [Li(TMEDA)]₂Pt(CH₂CMe₂CMe₂CH₂)₂ ( 1 ) revealed a new structure type of homoleptic organometallic compounds of platinum(II). Differences of the molecular structure of the “ate‐complex” [Li(TMEDA)]₂Pt(CH₂CH₂CH₂CH₂)₂ ( 2 ) as well as similarities to the structure of the homologeous “ate‐complex” of nickel(II) [Li(TMEDA)]₂Ni(CH₂CMe₂CMe₂CH₂)₂ ( 3 ) are described. A possible mechanism of the thermal decomposition of the complex 1 is discussed.     

Crystal Structures of (PPh3)2Pd(N3)2, (AsPh3)2Pd(N3)2, (2‐Chloropyridine)2Pd(N3)2, [(AsPh4)2][Pd2(N3)4Cl2], [(PNP)2][Pd(N3)4], [(AsPh4)2][Pt(N3)4] · 2 H2O,and [(AsPh4)2][Pt(N3)6]

The crystal structures of the monomeric palladium(II) azide complexes of the type L₂Pd(N₃)₂ (L = PPh₃ ( 1 ), AsPh₃ ( 2 ), and 2‐chloropyridine ( 3 )), the dimeric [(AsPh₄)₂][Pd₂(N₃)₄Cl₂] ( 4 ), the homoleptic azido palladate [(PNP)₂][Pd(N₃)₄] ( 5 ) and the homoleptic azido platinates [(AsPh₄)₂][Pt(N₃)₄] · 2 H₂O ( 6 ) and [(AsPh₄)₂][Pt(N₃)₆] ( 7 ) were determined by X‐ray diffraction at single crystals. 1 and 2 are isotypic and crystallize in the triclinic space group P1. 1 , 2 and 3 show terminal azide ligands in trans position. In 4 the [Pd₂(N₃)₄Cl₂]^2– anions show end‐on bridging azide groups as well as terminal chlorine atoms and azide ligands. The anions in 5 and 6 show azide ligands in equal positions with almost local C_4h symmetry at the platinum and palladium atom respectively. The metal atoms show a planar surrounding. The [Pt(N₃)₆]^2– anions in 7 are centrosymmetric (idealized S₆ symmetry) with an octahedral surrounding of six nitrogen atoms at the platinum centers.     

Synthese und Struktur der Nitrido‐Komplexe (PPh4)2[(O3Os≡N)2MCl2](M = Pd und Pt) und [{(Me2PhP)3Cl2Re≡N}2PdCl2]

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 C_i 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.     

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.     

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].     

Synthesis,Characterization, and Reactivity of Cationic Palladium(II) and Platinum(II) Iodo Complexes Containing a Linear or a Tripodal Aminophosphine. The X‐Ray Crystal Structures of [Pd{HN(CH2CH2PPh2)2}I]I and [Pd3{N(CH2CH2PPh2}3)2I4]I2

The complexes [M(PNHP)I]I (PNHP = bis[2‐(diphenylphosphino)ethyl]amine; M = Pd ( 1 ), Pt ( 2 )) and [M(NP₃)I]I (NP₃ = tris[2‐(diphenylphosphino)ethyl]amine; M = Pd ( 3 ), Pt ( 4 )) were prepared by interaction of the appropriate aminophosphine in CH₂Cl₂ with aqueous solutions containing [MCl₄]^2— salts and NaI in a ratio 1:4. Complexes 2 and 3 form the polynuclear compounds [Pt₂(PNHP)₃]I₄ ( 2a ) and [Pd₃(NP₃)₂I₄]I₂ ( 3a ) in the presence of coordinating solvents such as the mixture CD₃OD/D₂O/DMSO‐d₆ and CH₂Cl₂/CH₃OH, respectively. Complex 1 consists of distorted square‐planar cations [Pd(PNHP)I]⁺ and iodide anions able to establish short N‐H···I interactions of 2.850Å. The aminophosphine adopts a boat conformation and is coordinated to palladium in a tridentate chelating fashion. The crystal structure for cations of 3a reveals the presence of two types of distorted square‐planar Pd^II atoms, PdNP₂I and trans‐PdP₂I₂, NP₃ acting as tridentate chelating and bridging ligand, respectively. On the basis of ³¹P {¹H} NMR data it has been shown that each distorted square‐planar Pt(II) centre of 2a contains one PNHP acting as tridentate chelating ligand with the other aminophosphine bridging the two metals via the P atoms. Complexes 3 and 4 were shown by ³¹P {¹H} NMR to have the metal atom bound to the three P atoms of NP₃ and one iodo ligand. Additions of AcCysSH and GSH to 4 result, by a ring‐opening process, in the formation of [Pt(NP₂PO)(SR)] (RS = Acys ( 4a ), GS ( 4b )) in which the ligand contains a dangling arm phosphine oxide group and the platinum atom achieves the four‐coordination involving the N atom of the aminophosphine. Compounds [Pt₂(PNHP)₃]Cl₄ ( 2a′ , 2a″ ), [PtAu(PNHP)₂I]I₂ ( 2b ), and [Pt(PNHP)(ONO₂)](NO₃) ( 2c ) were detected in some extent in solution by reaction of complex 2 with Au(tdg)Cl (tdg = thiodiglycol), AuI and excess AgNO₃, respectively. While 1 does not react with AuI, complex 3 affords the heterobimetallic complexes PdCu(NP₃)I₃ ( 5 ), PdAg₂(NP₃)I₄ ( 6 ) and PdAu(NP₃)I₃ ( 7 ) by interaction with the appropriate iodide M′I (M′ = Cu, Ag, Au) via a chelate ring‐opening.     

{Ph2(Carb)P}MCl3 (M = Pd,Pt; Carb = 2,3-dihydro-1,3-diisopropyl-4,5dimethylimidazol-2-ylidene) – a Novel Cationic Phosphane Ligand [1]

The phosphane ligand [Ph₂(Carb)P]⁺ forms neutral complexes {Ph₂(Carb)P}MCl₃ (Carb = 2,3-dihydro-1,3-diisopropyl-4,5-dimethylimidazol-2-ylidene; M = Pd, Pt) through the reaction of it's chloride salt with (PhCN)₂MCl₂; the triarylphosphane type properties of the ligand are revealed by n.m.r. and structural data.     

Synthese und Kristallstrukturen von (3‐Methylpyridinium)3[DyCl6] und (3‐Methylpyridinium)2[DyCl5(Ethanol)]

Preparation and Structure of (3‐Methylpyridinium)₃[DyCl₆] and (3‐Methylpyridinium)₂[DyCl₅(Ethanol)] The complex chlorides (3‐Methylpyridinium)₃[DyCl₆] ( 1 ) and (3‐Methylpyridinium)₂[DyCl₅(Ethanol)] ( 2 ) have been prepared for the first time. The crystal structures have been determined from single crystal X‐ray diffraction data. 1 crystallizes in the trigonal space group R3c (Z = 36) with a = 2953.3(3) pm, b = 2953.3(3) pm and c = 3252.5(4) pm, compound 2 crystallizes in the triclinic space group P1 (Z = 2) with a = 704.03(8) pm, b = 808.10(8) pm, c = 1937.0(2) pm, α = 77.94(1)°, β = 87.54(1)° and γ = 83.26(1)°. The structures contain isolated octahedral building units [DyCl₆]^3– and [DyCl₅(Ethanol)]^2–, respectively.     

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.     

Stereochemically non-rigid transition metal complexes of 2,6-bis[(1-phenylimino) ethyl]pyridine (BIP) part 1. Dynamic NMR studies of [M(C6F5) 2(BIP)] (M = Pd or Pt)

The complexes [M(C₆F₅)₂(BIP)] (M = Pd^II or Pt^II, BIP = 2,6-bis[(1-phenylimino)ethyl]pyridine) have been synthesised and characterised as involving BIP as a bidentate chelate ligand. In solution they undergo 1,4 metallotropic shifts of the M(C₆ F₅)₂ moiety, E,Z isomerisation of the pendant imine bond, and restricted C-C rotation of the pendant portion of the BIP ligand. ¹H and ¹⁹F dynamic NMR studies yielded activation energies for these three types of fluxion. ΔG^≠ (298 K) values for the three processes were 89.6, 86.6 and 47.4kJmol⁻¹ respectively for the Pt^II complex. Values for the Pd^II complex were significantly lower in magnitude, namely 71.6, 70.4 and 41.8 kJ mol⁻¹ respectively.