Volume 52, Issue 8

Chloromethylchlorophosphines R(Cl)P-CH 2 -Cl (R = C 6 H 11 , sec-C 4 H 9 , 2,4,6-R′ 3 C 6 H 2 ; R′ = tBu, iPr) with bulky substituents (1a - 1d) have been prepared by treatment of Cl 2 P-CH 2 -Cl with organolithium compounds RLi (R = 2,4,6-R′ 3 C 6 H 2 ) or Grignard reagents RMgX (R = C 6 H 11 , sec-C 4 H 9 ). For the less bulky phenyl derivative Ph(Cl)P-CH 2 -Cl (1i) a protected group two stage synthesis has been developed employing Et 2 N(Cl)P-CH 2 -Cl as an intermediate. Si-N cleavage reactions between Cl 2 P-CH 2 -Cl and R 2 N-SiMe 3 or nucleophilic substitution with Ph 2 NH yield the amino derivatives R′ 2 N(Cl)P-CH 2 -Cl (R′ = Ph, Et, iPr) (1e, 1g, 1h). The chloromethylbromophosphines R(Br)P-CH 2 -Cl (R = Br, C 6 H 11 ) have been obtained by halogen exchange in 1 and 1a with MgBr 2 etherate. 1a, 1e, 1g and 1h exist preferably in an antiperiplanar conformation with respect to the P-C(H 2 ) bond as inferred from the analysis of the 1 H(CH 2 )-NMR spectra. Temperature dependent 1 H and 13 C { 1 H} NMR spectra indicate restricted rotational processes in 1h. On reaction of 2a with Fe 2 (CO) 9 the η 2 ,μ 3 -phosphaalkene cluster 3 is obtained, while with 2b (R = 2,4,6-iPr 3 C 6 H 2 ) the μ 3 -phosphinidene cluster 4 is formed. Reductive dehalogenation of 1c (R = 2,4,6-tBu 3 C 6 H 2 ) affords the phosphaalkene complex 6 in addition to the 2,3-dihydrobenzo[b]phosphole complex 5. Treatment of the iron carbonyl complex 7c with Fe 2 (CO) 9 in a 1:1 molar ratio at elevated temperatures leads to a novel μ 2 -phosphido complex 7b with an ortho-metallated Ph 2 N substituent.

The Madelung contribution to the lattice energy of simple binary crystal structures and lanthanide oxide fluorides with different types of disorder has been calculated by summation of Coulomb interactions and additional consideration of surface effects. In the case of NaCl, CsCl, ZnS and CaF 2 the agreement with mathematically exactly calculated values is better than 1 %. For the cubic high temperature modification of YOF it could be shown that a structure with long range order and short range disorder is more favourable from the energetic point of view than a stochastic distribution of the anions over all anion sites of the crystal.

The caesium hydrogen benzoylcyanoximate (L - ) complex with 18-crown-6 of composition Cs(18-crown-6){H(L) 2 } has been prepared and studied by means of X-ray diffraction [monoclinic, space group P2 1 /n, with a = 9.906(1), b = 18.387(3), c = 18.855(3)Å, β = 90.13(1)°, V = 3434.3(9) Å, Z = 4; final R1 = 0.043 for the 6431 independent reflections used. The lattice consists of Cs(18-crown-6) + cations and complex hydrogen oximate anions {H(L) 2 } - , formed via strong hydrogen bonding between the oxygen atoms of nitroso-groups [O - - - O ca. 2.456(5)Å]. The caesium atom deviates by 1.492(3) Å from the mean plane of the oxygen atoms of the macrocyclic ether (dominant orientation of disordered ligand, 60%) and adopts a typical “sunrise coordination” [Cs-O (ether) 3.040(9)-3.312(7) Å]. The hydrogen oximate groups are bonded to the metal center only on one side of the crown ether plane via the oxygen atoms of nitroso-groups and the nitrogen atoms of cyano groups (Cs-O ca. 3.040(9), 3.312(7) Å; Cs-N ca. 3.469(5), 3.679(6) Å). The coordination polyhedron of Cs + can be described as a distorted bicapped tetragonal prism.

P 4 O 8 was synthesized for the first time in a pure state. Its crystal structure has been refined using X-ray diffractometer data (monoclinic, C2/c with a = 970.0(2); b = 1017.9(2); c = 692.3(1) pm; β = 96.95(2)°; V = 678.5 Å 3 ; R 1 = 0.033; wR 2 = 0.073). Molecular geometry and packing in the solid state are discussed.

Sodium tetraisopropylcyclopentadienide (2) is attacked selectively in 5-position by tosyl azide with formation of 5-diazo-1,2,3,4-tetraisopropylcyclopentadiene (1) and also by the iminium salt [Me 2 NC(H)OMe] + MeOSO 3 - to yield 1,2,3,4-tetraisopropyl-6-dimethylamino-pentafulvene (3) with concomitant methanol elimination. In a one pot reaction 3 adds methyllithium to form a cyclopentadienide intermediate (4) which is converted in situ to 1,2,3,4- tetraisopropyl-6-methyl-pentafulvene (5) with dimethylchlorosilane. By the same procedure with 1,4-dilithiobutane instead of methyllithium two tetraisoproylfulvene moieties are linked to the bis-fulvene 8 with a -(CH 2 ) 4 - backbone. 3 can be converted directly to 1,2,3,4- tetraisopropylpentafulvene (7) with diisobutylaluminum hydride. 5 again adds methyllithium to give lithium pentaisopropylcyclopentadienide (6) or can be deprotonated at the 6-methyl group with potassium hydride. The intermediate potassium salt gives 1,2,3,4-tetraisopropyl- 6-trimethylsilylmethyl-pentafulvene (9) with trimethylchlorosilane. The fulvene 7 could be η 6 -coordinated to the tricarbonyl chromium complex 10 with [Cr(CO) 3 (NCEt) 3 ], 5 and 7 yield the molybdenum analogues 11 and 12 with [Mo(CO) 3 (NCEt) 3 ].

The molecular structure and X-as well as Q-band EPR studies of tetra-n-butylammonium-bis(1,1-dicyanoethene-2,2-dithiolato)nitrosyliron(I) enriched with 57 Fe are reported, (n-Bu 4 N) 2 [Fe(NO)(i-mnt)2] crystallizes triclinically, space group P1̄ with a = 9,5147(7) Å, b = 10,4841(8) Å, c = 25,840(2) Å, α= 92,510(1)°, β= 92,895(1)°, γ= 111,156(1)° , Z = 2. The g and the hyperfine coupling tensors A N and A Fe derived from the EPR spectra are rhombically-symmetric: g 1 = 2,043, g 2 = 2,039, g 3 = 2,031, A 1 N = 13,8·10 -4 cm -1 , A 2 N = 11,6·10 -4 cm -1 , A 3 N = 15,2·10 -4 cm -1 , A 1 Fe = 11,4·10 -4 cm -1 , A 2 Fe = 15,7·10 -4 cm -1 and A 3 Fe = -2,6·10 -4 cm -1 . The spin-density distribution within the first coordination sphere is discussed.

The hydrogenation of toluene over perovskites of composition La 0.8 Sr 0.2 Fe 1-x Co x O 3-z (x = 0.0, 0.2, 0.5, 0.8 and 1.0) is reported. The catalyst material has been prepared by the coprecipitation method using maleic acid as the complexing agent. The activity for the gas phase reaction of toluene and hydrogen at temperatures between 50 °C to 300 °C is reported for as-prepared and activated materials. The conversion has been found to be nearly temperature-independent over the as-prepared-per­ ovskites with a maximum of 40% conversion found for a composition La 0.8 Sr 0.2 Fe 0.5 Co 0.5 O 2.86 . Activation by an oxygen treatment at 500 °C was successful to enhance the activity of the Co-rich perovskites. All of these catalysts show a complete conversion of toluene at 100 °C, but activity decreases by time due to a reduction of the catalyst material. Again, La 0.8 Sr 0.2 Fe 0.5 Co 0.5 O 2.86 exhibits the slowest loss of activity. A model for its special properties is mainly attributed to the p-type conduction behaviour. The conversion behaviour of the perovskite type catalysts investigated here is compared to the results obtained with noble-metal supported catalysts and it can be concluded, that the perovskites exhibit higher conversion rates, maximum temperatures and higher cracking onset temperatures than these.

By reaction of [N(C 4 H 9 ) 4 ] 2 [B 12 H 12 ] with chlorotriphenyltin at 170 °C the phenylundecahydro-closo-dodecaborate anion [(C 6 H 5 )B 12 H 11 ] 2- is formed which can be isolated by ion exchange chromatography on diethylaminoethyl(DEAE) cellulose. The crystal structure of [As(C 6 H 5 ) 4 ] 2 [(C 6 H 5 )B 12 H 11 ] has been determined by single crystal X-ray diffraction analysis; triclinic, space group P1̄ with a = 11,0066(11), b = 11.1371(6), c = 22.236(2) Å, α = 93.040(6), β = 92.981(8), γ = 100.254(6)°, Z = 2. The 11 B NMR spectrum reveals the features (1:5:5:1) of a monosubstituated B 12 cage with the ipso B atom at - 6.1 and the antipodal B at -17.4 ppm. The 13 C and 1 H NMR spectra show the characteristic patterns of the phenyl group. The IR and Raman spectra exhibit characteristic BH stretching vibrations between 2464 and 2519 cm -1 and the CC stretching vibrations in the range of 1405 to 1592 cm -1 .

By reaction of (n-Bu 4 N) 2 [B 12 H 12 ] with 4-aminopyridine at 190°C the 4-aminopyridylundecahydro- closo-dodecaborate anion [(4-(NH)-C 5 H 4 N)B 12 H 11 ] - is obtained which can be separated from excess [B 12 H 12 ] 2- by ion exchange chromatography on diethylaminoethyl(DEAE) cellulose. The X-ray structure determination of (Ph 4 As)[(4-(NH)-C 5 H 4 N)B 12 H 11 ]-2CH 3 CN (orthorhombic, space group Pbca, a = 14.294(2), b = 19.587(2), c = 27.279(5)Å, Z = 8) reveals that the 4-aminopyridine substituent is bonded via the nitrogen atom of the amino group. The 11 B NMR spectrum exhibits the characteristic feature (1:5:5:1) of a monosubstituated B 12 cage with a downfield shift of ipso-B1 to -5.4 and antipodal-B12 to -18.1 ppm. The 1 H NMR spectrum reveals the pattern of a monosubstituated pyridine. The IR and Raman spectra exhibit characteristic BH stretching vibrations between 2489 and 2521 cm -1 and the CC and CN stretching vibrations in the range of 1405 to 1636 cm -1 .

The reaction of 2-chloro-3-(2-chloroethyl)-tetrahydro-2H-1,3,2-oxazaphosphorin-2-oxide 1 and 2-chloro-tetrahydro-2H-1,3,2-oxazaphosphorin-2-oxide 2 with 2-(trimethylsilyloxy)ethylamine 3 and bis-[2-(trimethylsiloxy)ethyl]amine 4, respectively, yielded the trimethylsilylated compounds 5 and 6, analogous to ifosfamide and cyclophosphamide. The reaction of 5 and 6 with 2-chloro-1,3,5-trimethyl-1,3,5-triaza-2-phosphorin-4,6-dione 7 led to the diphosphorus compounds 8 and 9 which could be transformed to ifosfamide 11 and cyclophosphamide 12 by treatment with sulfuryl chloride. This synthesis shows that the alkylating agents 2- chloroethylammonium chloride and bis-(2-chloroethyl)ammonium chloride can be avoided and the chlorine atom can be introduced in the final reaction step of the synthesis of 11 and 12.

Two equivalents of N-lithio-N-trimethylsilyl-amino-9-borabicyclo[3.3.1]nonane (1) react with tin and lead dichloride by salt elimination to give the corresponding bis(amino)stannylene 2 and -plumbylene 3, respectively. The compounds 2 and 3 are monomers in solution and were characterized by 1 H, 13 C, 14 N, 29 Si, 119 Sn and 207 Pb NMR spectroscopy.

Open lamellar structures 2 ∞ [Cu 4 I 4 {cyclo-(CH 3 AsO) 4 } 2 ] (1) and 2 ∞ [{CuX(CuX · CH 3 CN) 2 }{cyclo-(CH 3 AsO) 4 }] [X = Br (2), X =I (3)] may be prepared by self-assembly from CuX and methylcycloarsoxane (CH 3 AsO) n in acetonitrile solution at 100- 130 °C. Whereas 1 contains CU 4 I 4 oligomers consisting of three fused (Cul) 2 rings, 2 and 3 exhibit infinite 1 ∞ [CuX] single chains. An acceleration in the rate of heating between 20 and 100 °C from 2 °C h -1 to 5 °C h -1 for CuBr:As = 2:1 allows the isolation of the chain structure 1 ∞ [{(CuBr) 2 (CuBr · CH 3 CN) 2 {cyclo-(CH 3 AsO) 4 }] (4), as an intermediate product on the reaction pathway to 2. Compound 4 contains cage-like [Cu 4 Br 3 (AsO) 4 ] units in which the Cu and Br atoms belong to a 1 ∞ [Cu 2 Br 2 ] double chain containing fused (CuBr) 3 six-membered rings.

The preparation of the N,N-Bistrifluoromethylhydroxylammonium hexafluorometallates (CF 3 ) 2 N(X)OX + MF 6 - (X = H, D; M = As, Sb) is reported. The new compounds were characterized by IR, Raman, Mass, 1 H , 19 F and 13 C NMR spectroscopy. In addition we present our approach to the preparation of H-subsituted N,N-Bistrifluoromethylhydroxylammonium hexafluorometallates (CF 3 ) 2 N(Y)OH + MF 6 - (Y = CH 3 , Cl, F; M = As, Sb).

The crystal structures of trans-[OsCl 2 (acac) 2 ] (triclinic, space group P1̄, a = 7.4114(5), b = 7.6419(9), c = 7.9944(6) Å, α = 62.692(7), β = 87.687(6), γ = 60.667(6)°, Z = 1), trans-[OsBr 2 (acac) 2 ] (triclinic, space group P1̄, a = 7.467(3), b = 7.621(3), c = 8.260(3) Å, α = 115.03(3), β = 92.78(3), γ = 117.91(3)°, Z = 1), cis-[OsCl 2 (acac) 2 ] (monoclinic, space group C 2 /c, a = 13.8532(13), b = 7.7990(8), c = 13.6202(12) Å, β = 108.375(10)°, Z = 4) and cis-[OsBr 2 (acac) 2 ] (monoclinic, space group C 2 /c, a = 13.944(2), b = 8.0347(13), c = 13.743(2) Å, β = 106.757(12)°, Z = 4) have been determined by single crystal X-ray diffraction analysis. To enhance the spectroscopic resolution, the IR and Raman spectra of the six complexes have been measured at low temperature (10 K). Using the molecular parameters of the X-ray determinations normal coordinate analyses based on a modified valence force field have been performed for trans-[OsCl 2 (acac) 2 ], trans-[OsBr 2 (acac) 2 ] and cis-[OsCl 2 (acac) 2 ], and the normal modes of vibration assigned. With sets of 31 or 32 force constants, taking into account the innerligand vibrations, a good agreement between observed and calculated frequencies has been achieved. The valence force constants for the X-Os-X axes are f d (OsCl) = 1.81, f d (OsBr) =1.61 mdyn/Å, and for the Cl′-Os-O* axis are f d (OsCl’) = 1.94, f d (OsO*) = 2.81 mdyn/Å and f d (OsO) ranges from 3.27 to 3.31 mdyn/Å.

By reaction of [N(C 4 H 9 ) 4 ] 2 [B 10 H 10 ] with dichlorodiphenyltin in acetonitril at 80°C the 2- (dichlorophenyltin)-decaborate anion [2-SnCl 2 (C 6 H 5 )B 10 H 9 ] 2- is formed and can be isolated by ion exchange chromatography on diethylaminoethyl(DEAE) cellulose. The X-ray structure of [P(C 6 H 5 ) 4 ] 2 [2-SnCl 2 (C 6 H 5 )B 10 H 9 ] (triclinic, space group P1̄ with a = 11.2342(11), b = 11,2549(13), c = 22.265(6) Å, α = 89.478(14), β = 84.511(13), γ = 74.049(8)°) reveals that the SnCl 2 (C 6 H 5 ) substituent is bonded with a B2-Sn distance of 2.182(6) Å.

The structure of tetraphenylarsonium pentachlorocarbonylosmate(IV), (Ph 4 As)[OsCl 5 (CO)], the first example of a halogenocarbonyl complex with osmium in the oxidation state +IV, has been determined at 208 K by single crystal X-ray diffraction: tetragonal, space group P4/n with a = 12.821 , c = 8.084 Å, Z = 2. There are short intermolecular contacts between neighbouring anions along the tetragonal axis c and unusually large displacement ellipsoids of the carbonyl group and the four equatorial Cl ligands arising from a positional disorder of the complex anion. By analogy with a variety of reported structures of the (Ph 4 As)[RuNCl 4 ] structure type this is attributed to the close packing of the cation sublattice. Compared to other monocarbonylosmates the Os-C bond of 1.94(2) Å is extraordinaryly long while the bond between Os and the trans coordinated Cl ligand of 2.286(3) Å is rather short.

Single crystals of the new compound CaNi(VO)(PO 4 ) 2 have been prepared by solid state reactions below the melting point of the oxide mixture in evacuated quartz tubes. X-ray investigations led to orthorhombic symmetry, space group D 2h 16 -Pnma, a =14.113(1), b =6.408(1), c = 7.364(1) Å, Z = 4. The crystal structure shows 1 ∞ [NiO 4 ] and 1 ∞ [VO 6 P 2 O 3 ] polyhedra chains closely related to analogous chains in the isotypic compound CdV 2 O(PO 4 ) 2 . The short V -O distance of 1.66 Å indicates a vanadyl group as the main difference to CdV 2 O(PO 4 ) 2 . The short O-O distance of 2,395 Å of the edge-sharing PO 4 tetrahedra and VO 6 octahedra is discussed.

Single crystals of the compounds SrZn(VO)(PO 4 ) 2 (I) and BaCd(VO)(PO 4 ) 2 (II) have been prepared by solid state reactions in evacuated quartz tubes. X-ray investigations confirmed orthorhombic symmetry, space group D 15 2h -Pbca, lattice constants a/b/c (I): 9.066(1)/9.012(1)/17.513(1) Å and (II); 8.838(4)/8.915(4)/19.374(9) Å, Z = 8. Initially assumed isotypies of (I) and (II) to BaZn(VO)(PO 4 ) 2 proved to be erroneous considering significant details of the connectivity of the ZnO 4 and PO 4 tetrahedra (I) and the coordination sphere of cadmium (II), respectively. The similarities and differences of the crystal chemistry relation to (I) and (II) are discussed with respect to BaZn(VO)(PO 4 ) 2 . The Coulomb terms of the lattice energies of vanadyl M 2 (VO)(PO 4 ) 2 and divanadyl M(VO) 2 (PO 4 ) 2 phosphates are shown.

Single crystals of Ba 2,5 Cd 11 (VO 4 ) 9 have been prepared by solid state reactions. The new compound crystallizes with orthorhombic symmetry, space group D 14 2h -Pbcn, a = 20.842(6), b = 13.471(3), c = 11.838(9) Å, Z = 4. The crystal structure is characterized and dominated by CdO 6 octahedra and unusual square pyramids of O 2- around Cd 2+ forming a three-dimensional [Cd 11 O 36 ] network. The interstices are occupied by V 5+ and Ba 2+ ions. This results in VO 4 tetrahedra and irregular BaO 10 polyhedra isolated from each other. Occupation of the barium positions is deficient in agreement with the valence state V 5+ and calculations of the coulomb terms of lattice energy.

The oxidative degradation of a tricyclic dicarbonyl iron complex substituted at the diazaferrole ring by ester groups ( 1b ) does not lead to a bicyclic 1,2,3-diazepinone derivative, as reported recently for the case of the phenyl substituted compound (1a ), but affords the bicyclic 4-stilbenyl-1,2-dihydropyrazol-3-one 2b as shown by X-ray structural analysis. Since 1b is obtained by reaction of two different alkynes with a hexacarbonyldiiron complex of the cyclic 1,2-diazene, the over-all reaction formally consists of the addition of CO and two alkyne molecules to an N = N function affording a vinyl substituted diazacyclopentenone ring, and may be viewed as a type of hetero Pauson-Khand reaction.

The ternary title complex (2) is readily obtained by co-crystallization of 18-crown-6 (18C6) and di(4-carboxybenzenesulfonyl)amine (1) from hot water and was characterized by low-temperature X-ray diffraction. The crystal structure (triclinic, space group P1̄) displays one-dimensional polymeric sequences [(H 2 O) 2 ···18C6···(H 2 O) 2 ···{HN(SO 2 C 6 H 4 -4-COOH) 2 } 2 ] in which the molecules are associated through seven independent hydrogen bonds. The 18C6 ring lies on a crystallographic inversion centre and adopts the common pseudo-D 3d conformation. On both sides, the ring is flanked by a strongly hydrogen-bonded water dimer H 2 O-H-OH. This species forms three weak O-H-O bonds to alternating ether oxygen atoms and accepts a strong N-H-O bond from the adjacent acid dimer (1) 2 . The water dimers thus act as ideal donor-acceptor balancing links between the hexafunctional polyether and the monofunctional NH groups of the (1) 2 dimers. The (1) 2 dimer itself is formed by two symmetry related cyclic O-H···O interactions (both H disordered) of the well-known carboxylic acid dimer type. To this effect, molecule 1 adopts a folded, pseudo-C s symmetric conformation with stacked carboxyphenyl groups.

Reaction of bis[phthalocyaninato(2-)iridium(II)] ([(Irpc 2- ) 2 ]) with nitric oxide in pyridine yields nitrosyl-containing intermediates that are immediately oxidized by air yielding pyri-dine-nitro-phthalocyaninato(2-)iridium(III) ([Ir(py)(NO 2 )pc 2- ]). Linear-bis(triphenylphos-phine)iminium trans-bisnitro-phthalocyaninatoiridate(III) ( 1 (PNP) trans [Ir(NO 2 ) 2 pc 2- ]) is prepared by air-oxidation of [(Irpc 2- ) 2 ] in dichloromethane in the presence of (PNP)NO 2 . It crystallizes in the triclinic space group P1̄ (no. 2) with the following cell parameters: a =10.649(1) Å, b = 12.357(1) Å, c = 12.841(1) Å, α = 75.47(1)°, β = 67.88(1)°, γ = 65.31(1)°, Z = 1. Ir III is in the centre of a slightly waving pc 2- ligand coordinating two nitro ligands in an eclipsed fram-arrangement. The average Ir-N iso distance is 1.993(2) Å (N iso : isoindole N atom), the Ir-N distance is 2.189(3) Å (N: nitrite N atom), respectively. The structural data of the nitrite ion are: d(N-O) = 1.194(4) and 1.042(5) Å, ∠(O-N-O) = 131.7(4)°). Spectral properties with diagnostic IR absorption bands at 820, 1331 and 1398 cm -1 confirm the nitro coordination.

The mono-cyclopentadienyl metal complexes CpZrCl 3 (dme) and CpHfCl 3 (dme) react with acetone oxime in the presence of triethylamine to form the isotypic dinuclear complexes [CpMCl 2 ] 2 (μ-ONCMe 2 ) 2 (μ-HONCMe 2 ) (1: M = Zr; 2: M = Hf). 1 and 2 contain two oximato bridges and one oxime bridge. In the presence of water the reaction gives, with partial hydrolysis, the cyclic trinuclear compounds [CpZrCl] 3 (μ 3 -O)(μ 3 -OH)(μ-ONCMe 2 )3·½Me 2 CNOH (3) and [CpHfCl] 3 (μ 3 -O)(μ 3 -Cl)(μ-ONCMe 2 ) 3 ·CH 2 Cl 2 (4). In 1 to 4 the bridging oximato groups are side-on bonded via O and N to one metal atom and via (only) O to the other metal atom. The metal atoms of 1 to 4 exhibit an 18-electron configuration.

The signs of coupling constants [ 1 J( 195 Pt, 13 C) (> 0), 2 J( 195 Pt, 1 H) (< 0), ∑ 2 J ( 31 P, 13 C) trans + 2 J( 31 P, 13 C) cis (> 0) and ∑ 3 J( 31 P, 1 H ) trans + 3 J( 31 P, 1 H) cis (< 0)] in (ethene)bis(triphenylphosphane) platinum (0) (1) were determined by selective heteronuclear double and triple resonance experiments of the type 1 H{ 31 P}, 13 C{ 1 H, 31 P} and two-dimensional heteronuclear shift correlations (HETCOR) of the type 13 C/ 1 H, 195 Pt/ 1 H, and 31 P/ 1 H, either by observing the heteronucleus or 1 H in the more sensitive inverse mode.