Fragmentation reactions ofN-sulfinylaniline PhNSO by the dinuclear complex [Fe2(CO)7{μ-C(R)C(NEt2)}]: Nitrene and sulfur insertions into iron carbene bonds. Synthesis and x-ray structures of [Fe2(CO)6{μ-N(Ph)C(NEt2)C(Me)S}] [Fe2(CO)6{μ-N(Ph)C(NEt2)C(Ph)S}] · 0.5C6H14 and [Fe2(CO)6{μ-C(C3H5)C(NEt2)N(Ph)SO}] · 0.5CH2Cl2

The diiron ynamine complexes [Fe₂(CO)₇{μ-C(R)C(NEt₂)}] (1) (R=Me, Ph, C₃H₅, SiMe₃) react with theN-sulfinylaniline, PhNSO, in refluxing hexane to yield the complexes [Fe₂(CO)₆{μ-N(Ph)C(Me)S}] (2), [Fe₂(CO)₆{μ-N(Ph)C(NEt₂)C(Ph)S}] · 0.5C₆H₁₂ (3), [Fe₂(CO)₆{μ-C(C₃H₅)C(NEt₂)N(Ph)SO}] · 0.5CH₂Cl₂ (4), and [Fe₂(CO)₆{μ-C(SiMe₃)C(NEt₂)S)}] (5). Compound 5 was found to be identical to the previously reported product obtained from the reaction of 1 with sulfur. Compounds 2, 3, and 4 were characterized by single crystal X-ray diffraction analyses. Crystal data: for 2: space group = P2₁/n,a=9.533(1) Å,b=18.830(4) Å,c=12.705(4) Å, β=107.01(2)°,Z=4, 2687 reflections,R=0.027; for 3: space group=P2₁/n,a=13.660(2) Å,b=19.096(8) Å,c=10.972(2) Å, β=90.62(1)°,Z=4, 2821 reflections,R=0.036; for 4: space group=P2₁/a,a=18.098(5) Å,b=16.564(4) Å,c=18.548(2) Å, β=115.44(2)°,Z=4, 3569 reflections,R=0.041. Complexes 2 and 3 result from fragmentation of theN-sulfinylaniline ligand and insertion of the nitrene grouping into the Fe=C(aminocarbene) bond, whereas the sulfur atom inserts into one Fe-C bond of the bridging carbene. Compound 4 is formed by insertion of the entireN-sulfinyl aniline ligand into the Fe=C(aminocarbene) bond. All three complexes have basket-like arachno structure isolobal to the benzvalene one.     

[(CO)2(C5H5)Fe]2C60的合成与表征

有关 C6 0 取代的金属羰基化合物的研究方兴未艾 .C6 0 作为一个特殊的烯烃 ,以六元环间的碳碳双键提供电子对 ,与过渡金属羰基化合物形成诸如 η2 ,η4 ,η6等结构新颖的化合物约有 40多例 [1～ 5] ,但只有一例是以 Fe为中心原子的 C6 0 取代的金属羰基化合物 ( η2 - C6 0 ) Fe( CO) 4 [1] .本文报道了第一例 C6 0配位的 Fe的双核金属羰基化合物 [( CO) 2 ( C5H5) Fe]2 (η2 - C6 0 ) ,并通过元素分析 ,IR,1H NMR,13CNMR和 XPS进行表征 .1　实验部分[Fe( CO) 2 ( C5H5) ]2 购自 Aldrich公司 .C6 0 纯度为 99% .其余试剂均…     

(NEt(4))(2)[Fe(CN)(2)(CO)('S(3)')]: an iron thiolate complex modeling the [Fe(CN)(2)(CO)(S-Cys)(2)] site of [NiFe] hydrogenase centers

In the search for complexes modeling the [Fe(CN)(2)(CO)(cysteinate)(2)] cores of the active centers of [NiFe] hydrogenases, the complex (NEt(4))(2)[Fe(CN)(2)(CO)('S(3)')] (4) was found ('S(3)'(2-)=bis(2-mercaptophenyl)sulfide(2-)). Starting complex for the synthesis of 4 was [Fe(CO)(2)('S(3)')](2) (1). Complex 1 formed from [Fe(CO)(3)(PhCH=CHCOMe)] and neutral 'S(3)'-H(2). Reactions of 1 with PCy(3) or DPPE (1,2-bis(diphenylphosphino)ethane) yielded diastereoselectively [Fe(CO)(2)(PCy(3))('S(3)')] (2) and [Fe(CO)(dppe)('S(3)')] (3). The diastereoselective formation of 2 and 3 is rationalized by the trans influence of the 'S(3)'(2-) thiolate and thioether S atoms which act as pi donors and pi acceptors, respectively. The trans influence of the 'S(3)'(2-) sulfur donors also rationalizes the diastereoselective formation of the C(1) symmetrical anion of 4, when 1 is treated with four equivalents of NEt(4)CN. The molecular structures of 1, 3 x 0.5 C(7)H(8), and (AsPh(4))(2)[Fe(CN)(2)(CO)('S(3)')] x acetone (4 a x C(3)H(6)O) were determined by X-ray structure analyses. Complex 4 is the first complex that models the unusual 2:1 cyano/carbonyl and dithiolate coordination of the [NiFe] hydrogenase iron site. Complex 4 can be reversibly oxidized electrochemically; chemical oxidation of 4 by [Fe(Cp)(2)PF(6)], however, led to loss of the CO ligand and yielded only products, which could not be characterized. When dissolved in solvents of increasing proton activity (from CH(3)CN to buffered H(2)O), complex 4 exhibits drastic nu(CO) blue shifts of up to 44 cm(-1), and relatively small nu(CN) red shifts of approximately 10 cm(-1). The nu(CO) frequency of 4 in H(2)O (1973 cm(-1)) is higher than that of any hydrogenase state (1952 cm(-1)). In addition, the nu(CO) frequency shift of 4 in various solvents is larger than that of [NiFe] hydrogenase in its most reduced or oxidized state. These results demonstrate that complexes modeling properly the nu(CO) frequencies of [NiFe] hydrogenase probably need a [Ni(thiolate)(2)] unit. The results also demonstrate that the nu(CO) frequency of [Fe(CN)(2)(CO)(thiolate)(2)] complexes is more significantly shifted by changing the solvent than the nu(CO) frequency of [NiFe] hydrogenases by coupled-proton and electron-transfer reactions. The "iron-wheel" complex [Fe(6)[Fe('S(3)')(2)](6)] (6) resulting as a minor by-product from the recrystallization of 2 in boiling toluene could be characterized by X-ray structure analysis.     

A novel class of aryldiazene complexes: [(PPh3)2 (CO)IrCl(HNNC6H4R-p)(CCPh)] (BF4) (R = NO2, CN,COCH3)

In the reaction with phenylacetylene leading to [(PPh₃)₂(CO)IrCl (HNNC₆H₄R-p)(CCPh)] (BF₄) (R  NO₂, CN, COCH₃), the vacant coordination site in [(PPh₃)₂ (CO)IrCl(N₂C₆H₄ R-p)] (BF₄) plays a key role in the activation of the acetylenic CH bond. ca]To whom correspondence should be addressed.     

Bimetallic cyanide-bridged complexes based on the photochromic nitroprusside anion and paramagnetic metal complexes. Syntheses, structures, and physical characterization of the coordination compounds [Ni(en)2]4[Fe(CN)5NO]2[Fe(CN)6]x5H2O, [Ni(en)2][Fe(CN)5NO]x3H2O, [Mn(3-MeOsalen)(H2O)]2[Fe(CN)5NO], and [Mn(5-Brsalen)]2[Fe(CN)5NO

The synthesis, crystal structure, and physical characterization of the coordination compounds [Ni(en)2]4[Fe(CN)5NO]2[Fe(CN)6]x5H2O (1), [Ni(en)2][Fe(CN)5NO]x3H2O (2), [Mn(3-MeOsalen)(H2O)]2[Fe(CN)5NO] (3), and [Mn(5-Brsalen)]2[Fe(CN)5NO] (4) are presented. 1 crystallizes in the monoclinic space group P2(1)/n (a = 7.407(4) A, b = 28.963(6) A, c = 14.744(5) A, alpha = 90 degrees, beta = 103.26(4) degrees, gamma = 90 degrees, Z = 2). Its structure consists of branched linear chains formed by cis-[Ni(en)2]2+ cations and ferrocyanide and nitroprusside anions. The presence of two kinds of iron(II) sites has been demonstrated by M?ssbauer spectroscopy. 2 crystallizes in the monoclinic space group P2(1)/c (a = 11.076(3) A, b = 10.983(2) A, c = 17.018(5) A, alpha = 90 degrees, beta = 107.25(2) degrees, gamma = 90 degrees, Z = 4). Its structure consists of zigzag chains formed by an alternated array of cis-[Ni(en)2]2+ cations and nitroprusside anions. 3 crystallizes in the triclinic space group P1 (a = 8.896(5) A, b = 10.430(5) A, c = 12.699(5) A, alpha = 71.110(5) degrees, beta = 79.990(5) degrees, gamma = 89.470(5) degrees, Z = 1). Its structure comprises neutral trinuclear bimetallic complexes in which a central [Fe(CN)5NO]2- anion is linked to two [Mn(3-MeOsalen)]+ cations. 4 crystallizes in the tetragonal space group P4/ncc (a = 13.630(5) A, c = 21.420(8) A, Z = 4). Its structure shows an extended 2D neutral network formed by cyclic octameric [-Mn-NC-Fe-CN-]4 units. The magnetic properties of these compounds indicate the presence of quasi-isolated paramagnetic Ni2+ and Mn3+. Irradiated samples of the four compounds have been studied by differential scanning calorimetry to detect the existence of the long-lived metastable states of nitroprusside.     

On the reaction of Ph2PNHPPh2 with RNCS (R=Et, Ph, p-NO2C6H4): preparation of the zwitterionic ligand EtNHC(S)Ph2P==NPPh2C(S)NEt (HSNS) and the zwitterionic metalate [(SNS)Rh(CO)

The reaction of Ph(2)PNHPPh(2) (PNP) with RNCS (Et, Ph, p-NO(2)(C(6)H(4))) gives addition products resulting from the attack of the P atoms of PNP on the electrophilic carbon atom of the isothiocyanate. When PNP is reacted with EtNCS in a 1:2 molar ratio, the zwitterionic molecule EtNHC(S)PPh(2)==NP(+)Ph(2)C(S)N(-)Et (HSNS) is obtained in high yield. HSNS can be protonated (H(2)SNS(+)) or deprotonated (SNS(-)), behaving in the latter form as an S,N,S-donor pincer ligand. The reaction of HSNS with [(acac)Rh(CO)(2)] (acac=acetylacetonate) affords the zwitterionic metalate [(SNS)Rh(CO)]. Other products can be obtained depending on the R group, the PNP/RNCS ratio (1:1 or 1:2), and the reaction temperature. The proposed product of the primary attack of PNP on RNCS, Ph(2)PN==PPh(2)C(S)NHR (A), cannot be isolated. Reaction of A with another RNCS molecule leads to 1:2 addition compounds of the general formula RNHC(S)PPh(2)==NP(+)Ph(2)C(S)N(-)R (1), which can rearrange into the non-zwitterionic product RNHC(S)PPh(2)==NP(S)Ph(2) (2) by eliminating a molecule of RNC. Two molecules of A can react together, yielding 1:1 PNP/RNCS zwitterionic products of the formula RNHCH[PPh(2)==NP(S)Ph(2)]PPh(2)==NP(+)Ph(2)C(S)N(-)R (3). Compound 3 can then rearrange into RNHCH[PPh(2)==NP(S)Ph(2)](2) (4) by losing a RNC molecule. When R=Et (a), compounds 1 a, 2 a (HSNS), and 4 a have been isolated and characterized. When R=Ph (b), compounds 2 b and 4 b can be prepared in high yield. When R=p-NO(2)C(6)H(4) (c), only compound 3 c is observed and isolated in high yield. The crystal structures of HSNS, [(SNS)Rh(CO)], and of the most representative products have been determined by X-ray diffraction methods.     

Improved preparation of h5-C5H5 Fe(CO)2(h1-alkyl) complexes from [h5-C5H5Fe(CO)2(h2-alkene)]+BF4−

Sodium cyanoborohydride has been found to be very effective for the conversion of [(h⁵-C₅H₅)Fe(CO)₂(h²-alkene)]⁺BF₄^? complexes to the corresponding h¹-alkyl derivatives.     

Metal dimers as catalysts : III. The reaction between Fe(CO)5, and group V donor ligands in the presence of [(η5-C5H4R)Fe(CO)222]2 (R  H,Me) and [(η5-C5Me5)Fe(CO)2]2 as catalyst

The reaction between Fe(CO)₅, and group V donor ligands L, (L  PPh₃, AsPh₃, SbPh₃, PMePh₂, PMe₂Ph, Asme₂Ph, P(C₆H₁₁)₃, P(n-Bu)₃, P(i-Bu)₃, P(OPh)₃, P(OEt)₃, P(OMe)₃) in the presence of [(η⁵-C₅Me₅Fe(CO)₂]₂ (R  H, Me) or [(η⁵-C₅Me₅)Fe(CO)₂]₂ as catalyst in refluxing toluene, rapidly gives the complexes Fe(CO)₄L in yields > 85%. The reaction rate is essentially independent of the nature of L for [(η₅-C₅Me₅)Fe(CO)₂]₂ as catalyst. For the other catalysts, the rate is influenced predominantly by the steric properties of L. These results are interpreted in terms of the interaction between the catalyst and the ligand L to give derivatives of the type (η⁵-C₅H₄R)₂Fe₂,(CO)₃,(L). These derivatives were also found to catalyse the reaction between Fe(CO)₅, and L. The complexes [(η-C₅H₄R)Fe(CO)₂]₂ (R  H, Me) and [(η⁵-C₅Me₅)Fe(CO)₂]₂ also catalyse the reaction between Mn₂(CO)₁₀ and PPh₃ to give Mn₂(CO)₈- PPh₃)₂ in > 80% yield.     

Mn7O5(OR)2(O2CPh)9(terpy)] (R = Me, CH2Ph) complexes with a fused cubane/butterfly core and an S = 6 ground-state spin

Two new heptanuclear Mn clusters, [Mn7O5(OMe)2(O2CPh)9(terpy)] (1) and [Mn7O5(OCH2Ph)2(O2CPh)9(terpy)] (2), were prepared from the partial alcoholysis of the trinuclear complex [Mn3O(O2CPh)6(py)2(H2O)] (3) in the presence of terpy (terpy = 2,2':6',2' '-terpyridine). Complexes 1 and 2 crystallize in the triclinic P and the orthorhombic Pbca space groups, respectively. The clusters are both mixed valent, containing three Mn oxidation states: MnIV, 5MnIII, and MnII. The Mn ions are held together by nine doubly bridging benzoates, four mu3-O2- ions, one mu5-O2- ion, and either two mu-MeO- (1) or two mu-PhCH2O- (2) groups. The single terpy chelate in each complex is attached to the MnII ion. The core topology is novel and very unusual, comprising a cubane and a butterfly unit fused by sharing a MnIII and the mu5-O2- ion. Solid-state dc and ac magnetic susceptibility studies establish that complexes 1 and 2 both possess an S = 6 ground-state spin. Fits of variable-temperature and -field magnetization data gave S = 6, g = 1.88, and D = -0.21 cm-1 for 1 and S = 6, g = 1.86, and D = -0.18 cm-1 for 2. Single-crystal magnetization vs dc field scans down to 0.1 K for 2 show only very little hysteresis at 0.1 K.     

Über den Phosphandiyl‐Transfer von invers‐polarisierten Phosphaalkenen R1P=C(NMe2)2 (R1 = tBu,Cy, Ph,H) auf Phospheniumkomplexe [(η5‐C5H5)(CO)2M=P(R2)R3] (R2 = R3 = Ph; R2 = tBu,R3 = H; R2 = Ph,R3 = N(SiMe3)2)

Phosphanediyl Transfer from Inversely Polarized Phosphaalkenes R¹P=C(NMe₂)₂ (R¹ = tBu, Cy, Ph, H) onto Phosphenium Complexes [(η⁵‐C₅H₅)(CO)₂M=P(R²)R³] (R² = R³ = Ph; R² = tBu, R³ = H; R² = Ph, R³ = N(SiMe₃)₂) Reaction of the freshly prepared phosphenium tungsten complex [(η⁵‐C₅H₅)(CO)₂W=PPh₂] ( 3 ) with the inversely polarized phosphaalkenes RP=C(NMe₂)₂ ( 1 ) ( a : R = tBu; b : Cy; c : Ph) led to the η²‐diphosphanyl complexes ( 9a‐c ) which were isolated by column chromatography as yellow crystals in 24‐30 % yield. Similarly, phosphenium complexes [(η⁵‐C₅H₅)(CO)₂M=P(H)tBu] (M = W ( 6 ); Mo ( 8 )) were converted into (M = W ( 11 ); Mo ( 12 )) by the formal abstraction of the phosphanediyl [PtBu] from 1a . Treatment of [(η⁵‐C₅H₅)(CO)₂W=P(Ph)N(SiMe₃)₂] ( 4 ) with HP=C(NMe₂)₂ ( 1d ) gave rise to the formation of yellow crystalline ( 10 ). The products were characterized by elemental analyses and spectra (IR, ¹H, ¹³C‐, ³¹P‐NMR, MS). The molecular structure of compound 10 was elucidated by an X‐ray diffraction analysis.     

Transition metal-main group metal bond. VI. 199Hg NMR and 57Fe mössbauer study of (η5-C5H5)(CO)2FeHgX [X = Cl,Br,I,S2COC2H5, S2CN(C2H5)2, S2P(OC2H5)2 and Fe(CO)2(η5-C5H5)]complexes.

The ¹⁹⁹Hg NMR and ⁵⁷Fe Mössbauer spectra of iron-mercury bounded complexes are reported, compared with the ¹⁹⁹Hg NMR data for analogous molybdenum and tungsten compounds and discussed in terms of the polarization of the metal-metal bonds.     

Synthesis and X-ray crystal structure of complexes Cp(CO)2MnP(SR)3 (R = Pri,Ph)

Cp(CO)₂Mn · THF reacts in THF with thiosters of phosphorus acid, P(SR)₃, to give new complexes Cp(CO)₂MnP(SR)₃ in which the manganese atom is coordinated to the phosphorus atom. The X-ray crystal structure of compounds with R = Prⁱ and Ph was established. The metal atom has a coordination enviroment of the three-legged piano stool type. The bond angles OC-Mn-CO and OC-Mn-P are 90.6–95.9(4)°. Bond distances are: Mn-P 2.188(2) and 2.171(2) E, P-S 2.097(3)-2.137(3) E.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1116–1119, June, 1994.This work was carried out with financial support from the Russian Foundation for Basic Research (Project No.93-03-5830).