Synthesis, structural characterization, reactivity, and thermal stability of [eta(5):sigma-Me2C(C5H4)(C2B10H10)]Ti(R)(NMe2)

Reaction of [eta:(5)sigma-Me2C(C5H4)(C2B10H10)]TiCl(NMe2) (1) with 1 equiv of PhCH2K, MeMgBr, or Me3SiCH2Li gave corresponding organotitanium alkyl complexes [eta:(5)sigma-Me2C(C5H4)(C2B10H10)]Ti(R)(NMe2) (R = CH2Ph (2), CH2SiMe3 (4), or Me (5)) in good yields. Treatment of 1 with 1 equiv of n-BuLi afforded the decomposition product {[eta:(5)sigma-Me2C(C5H4)(C2B10H10)]Ti}2(mu-NMe)(mu:sigma-CH2NMe) (3). Complex 5 slowly decomposed to generate a mixed-valence dinuclear species {[eta:(5)sigma-Me2C(C5H4)(C2B10H10)]Ti}2(mu-NMe2)(mu:sigma-CH2NMe) (6). Complex 1 reacted with 1 equiv of PhNCO or 2,6-Me2C6H3NC to afford the corresponding monoinsertion product [eta:(5)sigma-Me2C(C5H4)(C2B10H10)]Ti(Cl)[eta(2)-OC(NMe2)NPh] (7) or [eta:(5)sigma-Me2C(C5H4)(C2B10H10)]Ti(Cl)[eta(2)-C(NMe2)=N(2,6-Me2C6H3)] (8). Reaction of 4 or 5 with 1 equiv of R'NC gave the titanium eta(2)-iminoacyl complexes [eta:(5)sigma-Me2C(C5H4)(C2B10H10)]Ti(NMe2)[eta(2)-C(R)=N(R')] (R = CH2SiMe3, R' = 2,6-Me2C6H3 (9) or tBu (10); R = Me, R' = 2,6-Me2C6H3 (11) or tBu (12)). The results indicated that the unsaturated molecules inserted into the Ti-N bond only in the absence of the Ti-C(alkyl) bond and that the Ti-C(cage) bond remained intact. All complexes were fully characterized by various spectroscopic techniques and elemental analyses. Molecular structures of 2, 3, 6-8, and 10-12 were further confirmed by single-crystal X-ray analyses.     

Protonation of a lanthanum phosphide-alkyl occurs at the P-La not the C-La bond: isolation of a cationic lanthanum alkyl complex

Protonation of the heteroleptic, cyclometalated lanthanum phosphide complex [((Me3Si)2CH)(C6H4-2-CH2NMe2)P]La(THF)[P(C6H4-2-CH2NMe2)(CH(SiMe3)(SiMe2CH2))] with [Et3NH][BPh4] yields the cationic alkyllanthanum complex [(THF)4La[P(C6H4-2-CH2NMe2)(CH(SiMe3)(SiMe2CH2))]][BPh4].     

Palladium(II) and platinum(II) complexes with tridentate iminophosphine ligands; synthesis and structural studies

The previously synthesised Schiff-base ligands 2-(2-Ph(2)PC(6)H(4)N[double bond, length as m-dash]CH)-R'-C(6)H(3)OH (R'= 3-OCH(3), HL(1); 5-OCH(3), HL(2); 5-Br, HL(3); 5-Cl, HL(4)) were prepared by a faster, more efficient route involving a microwave assisted co-condensation of 2-(diphenylphosphino)aniline with the appropriate substituted salicylaldehyde. HL(1-4) react directly with M(II)Cl(2)(M = Pd, Pt) or Pt(II)I(2)(cod) affording neutral square-planar complexes of general formula [M(II)Cl(eta(3)-L(1-4))](M = Pd, Pt, 1-8) and [Pt(II)I(eta(3)-L(1-4))](M = Pd, Pt, 9-12). Reaction of complexes 1-4 with the triarylphosphines PR(3)(R = Ph, p-tolyl) gave the novel ionic complexes [Pd(II)(PR(3))(eta(3)-L(1-4))]ClO(4)(13-20). Substituted platinum complexes of the type [Pt(II)(PR(3))(eta(3)-L(1-4))]ClO(4)(R = P(CH(2)CH(2)CN)(3)21-24) and [Pt(II)(P(p-tolyl)(3))(eta(3)-L(3,4))]ClO(4)( 25 and 26 ) were synthesised from the appropriate [Pt(II)Cl(eta(3)-L(1-4))] complex (5-8) and PR(3). The complexes are characterised by microanalytical and spectroscopic techniques. The crystal structures of 3, 6, 10, 15, 20 and 26 were determined and revealed the metal to be in a square-planar four-coordinate environment containing a planar tridentate ligand with an O,N,P donor set together with one further atom which is trans to the central nitrogen atom.     

Structural basis for unusually long wavelength charge transfer transitions in complexes [MCl(ECH(2)CH(2)NMe(2))(PR(3))] (E = Te,Se; M = Pt,Pd): experimental results and TD-DFT calculations

A series of new complexes, the blue compounds [PdCl(TeCH(2)CH(2)NMe(2))(PR(3))] (PR(3) = PEt(3), PPr(n)(3), PBu(n)(3), PMe(2)Ph, PMePh(2), PPh(3), PTol(3)) and the red [PtCl(TeCH(2)CH(2)NMe(2))(PR(3))] (PR(3) = PMe(2)Ph, PMePh(2)), were synthesized and studied spectroscopically ((1)H and (31)P NMR, UV/vis) and by cyclic voltammetry. The structures of [PdCl(TeCH(2)CH(2)NMe(2))(PPr(n)(3))] (2b) [PdCl(TeCH(2)CH(2)NMe(2))(PMePh(2))] (2e), [PtCl(TeCH(2)CH(2)NMe(2))(PMePh(2))] (2i), and the related [PtCl(SeCH(2)CH(2)NMe(2))(PEt(3))] (3) were determined crystallographically, revealing a typical pattern of trans-positioned neutral N and P donor atoms in an approximately square planar setting. The molecules 2b, 2e, and 2i were calculated by TD-DFT methodology to understand the origin of the weak (epsilon approximately 200 M(-1) cm(-1)) long-wavelength bands at about 600 nm for Pd/Te complexes such as 2b or 2e, at ca. 460 nm for Pt/Te systems such as 2i, and at about 405 nm for Pt/Se analogues such as 3. These transitions are identified as charge transfer transitions from the selenolato or tellurolato centers to unoccupied orbitals involving mainly the phosphine coligands for the Pt(II) compounds and more delocalized MOs for the Pd(II) analogues. Calculations and electrochemical data were used to rationalize the effects of metal and chalcogen variation.     

Pyrazolylcyclotriphosphazene containing pendant polymers: synthesis,characterization, and phosphate ester hydrolysis using a Cu(II)-metalated cross-linked polymeric catalyst

A multi-pyrazolyl cyclotriphosphazene containing polymerizable group N(3)P(3)(3,5-Me(2)Pz)(5)(O-C(6)H(4)-p-C(6)H(4)-p-CH=CH(2)) (2) has been prepared from the corresponding chloro derivative N(3)P(3)Cl(5)(O-C(6)H(4)-p-C(6)H(4)-p-CH=CH(2)) (1). The X-ray structures of 1 and 2 have been determined. Compound 2 undergoes ready metalation with CuCl(2) to afford N(3)P(3)(3,5-Me(2)Pz)(5)(O-C(6)H(4)-p-C(6)H(4)-p-CH=CH(2)).CuCl(2) (3). Model compound N(3)P(3)(3,5-Me(2)Pz)(5)(O-C(6)H(4)-p-CHO).CuCl(2) (6) has been prepared and characterized by spectroscopy and X-ray crystallography. In this compound, the coordination around copper is distorted trigonal bipyramidal, and the cyclotriphosphazene coordinates in a non-gem N(3) mode. Compound 2 has been copolymerized with divinylbenzene to afford cross-linked multisite coordinating polymer CPPL which is readily metalated with CuCl(2) to afford copper-containing polymer CPPL-Cu. The coordination environment around copper in CPPL-Cu has been evaluated by obtaining its EPR, optical, and IR spectra and comparing them with those of model compounds 3 and 6. The utility of CPPL-Cu as a heterogeneous catalyst has been demonstrated in the phosphate ester hydrolysis involving three model phosphate esters: p-nitrophenyl phosphate (pNPP), bis(p-nitrophenyl) phosphate (bNPP), and 2-(hydroxypropyl)-p-nitrophenyl phosphate (hNPP). In all of these reactions, a significant rate enhancement of ester hydrolysis is observed. Detailed kinetic analyses to evaluate Michaelis-Menten parameters have also been carried out along with experiments to elucidate the effect of pH, solvent, and temperature on the rate of hydrolysis. Recycling experiments on the hydrolysis of pNPP with CPPL-Cu shows that it can be recycled several times over without affecting the rates.     

Coordination algorithms control molecular architecture: [CuI4(L2)4]4+ grid complex versus [MII2(L2)2X4]y+ side-by-side complexes (M=Mn,Co, Ni,Zn; X=solvent or anion) and [FeII(L2)3][Cl3FeIIIOFeIIICl3

The synthesis and characterisation of a pyridazine-containing two-armed grid ligand L2 (prepared from one equivalent of 3,6-diformylpyridazine and two equivalents of p-anisidine) and the resulting transition metal (Zn, Cu, Ni, Co, Fe, Mn) complexes (1-9) are reported. Single-crystal X-ray structure determinations revealed that the copper(I) complex had self-assembled as a [2 x 2] grid, [Cu(I) (4)(L2)(4)][PF(6)](4).(CH(3)CN)(H(2)O)(CH(3)CH(2)OCH(2)CH(3))(0.25) (2.(CH(3)CN)(H(2)O)(CH(3)CH(2)OCH(2)CH(3))(0.25)), whereas the [Zn(2)(L2)(2)(CH(3)CN)(2)(H(2)O)(2)][ClO(4)](4).CH(3)CN (1.CH(3)CN), [Ni(II) (2)(L2)(2)(CH(3)CN)(4)][BF(4)](4).(CH(3)CH(2)OCH(2)CH(3))(0.25) (5 a.(CH(3)CH(2)OCH(2)CH(3))(0.25)) and [Co(II) (2)(L2)(2)(H(2)O)(2)(CH(3)CN)(2)][ClO(4)](4).(H(2)O)(CH(3)CN)(0.5) (6 a.(H(2)O)(CH(3)CN)(0.5)) complexes adopt a side-by-side architecture; iron(II) forms a monometallic cation binding three L2 ligands, [Fe(II)(L2)(3)][Fe(III)Cl(3)OCl(3)Fe(III)].CH(3)CN (7.CH(3)CN). A more soluble salt of the cation of 7, the diamagnetic complex [Fe(II)(L2)(3)][BF(4)](2).2 H(2)O (8), was prepared, as well as two derivatives of 2, [Cu(I) (2)(L2)(2)(NCS)(2)].H(2)O (3) and [Cu(I) (2)(L2)(NCS)(2)] (4). The manganese complex, [Mn(II) (2)(L2)(2)Cl(4)].3 H(2)O (9), was not structurally characterised, but is proposed to adopt a side-by-side architecture. Variable temperature magnetic susceptibility studies yielded small negative J values for the side-by-side complexes: J=-21.6 cm(-1) and g=2.17 for S=1 dinickel(II) complex [Ni(II) (2)(L2)(2)(H(2)O)(4)][BF(4)](4) (5 b) (fraction monomer 0.02); J=-7.6 cm(-1) and g=2.44 for S= 3/2 dicobalt(II) complex [Co(II) (2)(L2)(2)(H(2)O)(4)][ClO(4)](4) (6 b) (fraction monomer 0.02); J=-3.2 cm(-1) and g=1.95 for S= 5/2 dimanganese(II) complex 9 (fraction monomer 0.02). The double salt, mixed valent iron complex 7.H(2)O gave J=-75 cm(-1) and g=1.81 for the S= 5/2 diiron(III) anion (fraction monomer=0.025). These parameters are lower than normal for Fe(III)OFe(III) species because of fitting of superimposed monomer and dimer susceptibilities arising from trace impurities. The iron(II) centre in 7.H(2)O is low spin and hence diamagnetic, a fact confirmed by the preparation and characterisation of the simple diamagnetic iron(II) complex 8. M?ssbauer measurements at 77 K confirmed that there are two iron sites in 7.H(2)O, a low-spin iron(II) site and a high-spin diiron(III) site. A full electrochemical investigation was undertaken for complexes 1, 2, 5 b, 6 b and 8 and this showed that multiple redox processes are a feature of all of them.     

A homologous series of alkaline earth phosphanides: syntheses,crystal structures,and unusual dynamic behavior of (THF)(n)M[P(CH(SiMe(3))(2))(C(6)H(4)-2-CH(2)NMe(2))](2) (M = Mg,Ca, Sr,Ba)

The secondary phosphine R(Me(2)NCH(2)-2-C(6)H(4))PH reacts with Bu(2)Mg to give the homoleptic complex Mg[PR(C(6)H(4)-2-CH(2)NMe(2))](2) (1) [R = CH(SiMe(3))(2)]. The analogous heavier alkaline earth metal complexes (THF)(n)Ae[PR(C(6)H(4)-2-CH(2)NMe(2))](2) [Ae = Ca (2), n = 0; Ae = Sr (3), Ba (4), n = 1] have been synthesized by metathesis reactions between K[PR(C(6)H(4)-2-CH(2)NMe(2))] and 0.5 equiv of the respective alkaline earth metal diiodide. Compounds 1-4 have been characterized by X-ray crystallography and multielement NMR spectroscopy. In the solid state, compounds 1-4 are monomeric, complexes 1 and 2 adopting a distorted tetrahedral geometry and complexes 3 and 4 adopting a distorted square pyramidal geometry (1: orthorhombic, P2(1)2(1)2(1), a = 11.413(3) A, b = 12.072(3) A, c = 32.620(11) A, Z = 4. 2: monoclinic, P2(1)/c, a = 9.5550(4) A, b = 17.4560(7) A, c = 24.5782(10) A, beta = 91.673(2) degrees, Z = 4. 3: monoclinic, C2/c, a = 15.0498(9) A, b = 13.0180(8) A, c = 24.3664(14) A, beta = 104.593(2) degrees, Z = 4. 4: monoclinic, C2/c, a = 15.2930(10) A, b = 13.0326(9) A, c = 24.6491(17) A, beta = 105.542(2) degrees, Z = 4). In toluene solution, compounds 2-4 are subject to dynamic processes which are attributed to a monomer-dimer equilibrium for which bridge-terminal exchange of the phosphanide ligands in the dimer may be frozen out at low temperatures.     

Carbophosphazene-supported ligand systems containing pyrazole/guanidine coordinating groups

Carbophosphazene-based coordination ligands [{NC(NMe(2))}(2){NP(3,5-Me(2)Pz)(2)}] (1), [{NC(NEt)(2)}{NC(3,5-Me(2)Pz)}{NP(3,5-Me(2)Pz)(2)}] (2), [NC(3,5-Me(2)Pz)](2)[NP(3,5-Me(2)Pz)(2)] (3), [{NCCl}(2){NP(NC(NMe(2))(2))(2)}] (4), and [{NC(p-OC(5)H(4)N)}(2){NP(NC(NMe(2))(2))(2)}] (5) were synthesized and structurally characterized. In these compounds, the six-membered C(2)N(3)P ring is perfectly planar. The reaction of 1 with CuCl(2) afforded [{NC(NMe(2))}(2){NHP(O)(3,5-Me(2)Pz)}·{Cu(3,5-Me(2)PzH)(2)(Cl)}][Cl] (6). The ligand binds to Cu(II) utilizing the geminal [P(O)(3,5-Me(2)Pz)] coordinating unit. Similarly, the reaction of 2 with PdCl(2) afforded, after a metal-assisted P-N hydrolysis, [{NC(NEt)(2)}{NC(3,5-Me(2)Pz)}{NP(O)(3,5-Me(2)Pz)}·{Pd(3,5-Me(2)PzH)(Cl)}] (7). In the latter, the [P(O)(3,5-Me(2)Pz)] unit does not coordinate; in this instance, the Pd(II) is bound by a ring nitrogen atom and a carbon-tethered pyrazolyl nitrogen atom. The reaction of 3 with PdCl(2) also results in P-N bond hydrolysis affording [{NC(3,5-Me(2)Pz)(2)}{NP(O)(3,5-Me(2)Pz)}{Pd(Cl)}] (8). In contrast to 7, however, in 8, the Pd(II) elicits a nongeminal η(3) coordination from the ligand involving two carbon-tethered pyrazolyl groups and a ring nitrogen atom. Metalated products could not be isolated in the reaction of 3 with K(2)PtCl(4). Instead, a P-O-P bridged carbodiphosphazane dimer, [{NC(3,5-Me(2)Pz)NHC(3,5-Me(2)Pz)}{NP(O)}](2) (9), was isolated as the major product. Finally, the reaction of 5 with PdCl(2) resulted in [{NC(OC(5)H(4)N)}(2){NP(NC(NMe(2))(2))(2)}·{PdCl(2)}] (10). In the latter, the exocyclic P-N bonds are quite robust and are involved in binding to the metal ion. Compounds 6-10 have been characterized by a variety of techniques including X-ray crystallography. In all of the compounds, the bond parameters of the inorganic heterocyclic rings are affected by metalation.     

Syntheses and crystal structures of the closo-borates M2[B7H7] and M[B7H8] (M = PPh4, PNP, and N(n-Bu4)): the missing crystal structure in the series [B(n)H(n)]2- (n = 6-12)

Oxidation of [N(n-Bu(4))](2)[B(9)H(9)] with oxygen in a mixture of dimethoxyethane and CH(2)Cl(2) leads to salts of the [B(7)H(7)](2-) dianion. This is the first convenient synthesis for a seven-vertex hydro-closo-borate anion. Protonation with NEt(3)·HCl resulted in salts of the [B(7)H(8)](-) monoanion. Both closo-borate anions were isolated and characterized by (1)H, (1)H{(11)B}, (11)B, and (11)B{(1)H} NMR spectroscopy. The temperature-dependent (1)H{(11)B}, (11)B, and (11)B{(1)H} NMR spectra of [B(7)H(8)](-) were also measured. The structure of [B(7)H(7)](2-) as well as of [B(7)H(8)](-) were determined by single-crystal X-ray diffraction.     

Synthesis of tris- and tetrakis(pyrazol-1-yl)borate gold(III) complexes. Crystal structures of [Au[kappa(2)-N,N'-BH(Pz)(3)]Cl(2)] (pz = pyrazol-1-yl) and [Au[kappa(2)-N,N'-B(Pz)(4)](kappa(2)-C,N-C(6)H(4)CH(2)NMe(2)-2)]ClO(4).CHCl(3)

Na[BH(pz)(3)] and Na[AuCl(4)].2H(2)O react in water (1:1) to give [Au[kappa(2)-N,N'-BH(pz)(3)]Cl(2)] (1) or, in the presence of NaClO(4) (2:1:1), the cationic complex [Au[kappa(2)-N,N'-BH(pz)(3)](2)]ClO(4) (2). The reactions of Na[B(pz)(4)] with the cyclometalated gold complexes [AuRCl(2)] and NaClO(4) (1:1:1) produce [Au[kappa(2)-N,N'-B(pz)(4)](R)]ClO(4) [R = kappa(2)-C,N-C(6)H(4)CH(2)NMe(2)-2 (3)] or [Au[kappa(2)-N,N'-B(pz)(4)](R)Cl] [R = C(6)H(3)(N=NC(6)H(4)Me-4')-2-Me-5 (4)], respectively, although 4 is better obtained in the absence of NaClO(4). The crystal structures of 1 and 3.CHCl(3) are reported. Both complexes display the gold center in square planar environments, two coordination sites being occupied by the chelating poly(pyrazolyl)borate ligands.     

New molecular assemblies of redox isomers, [CrIII(X4SQ)3-n(X4Cat)n]-n (X = Cl and Br; n = 0, 1, and 2), with metallocenium cations, [MIIICp2]+ (M = Co and Fe): X-ray crystal structures and physical properties

A series of redox isomers of [CrIII(X4SQ)(X4Cat)2]2-, [CrIII(X4SQ)2(X4Cat)]-, and [CrIII(X4SQ)3]0 (X = Cl and Br, SQ = semiquinonate, and Cat = catecholate) have been synthesized and characterized as charge-transfer (CT) compounds with metallocenium cations: (CoIIICp2)2[CrIII(Cl4SQ)(Cl4Cat)2] (1), (CoIIICp2)2[CrIII(Br4SQ)(Br4Cat)2] (2), (FeIIICp2)[CrIII(Cl4SQ)2(Cl4Cat)].C6H6 (4), (FeIIICp2)[CrIII(Br4SQ)2(Br4Cat)].CS2 (5), and (FeIIICp2)[CrIII(Cl4SQ)2(Cl4Cat)][CrIII(Cl4SQ)3] (6). First, the oxidation states of the chromium complexes are strongly dependent on the redox potentials of the metallocenes used. The CoIICp2, exhibiting stronger reduction power than FeIICp2, is useful for two-electron reduction of the [CrIII(X4SQ)3]0, affording [CrIII(X4SQ)(X4Cat)2]2- (1 and 2), which are first isolated and crystallographically characterized in the solid state. In contrast the reaction with FeIICp2 affords only [CrIII(X4SQ)2(X4Cat)]- (4 and 5). Second, solvents influence crystal structures of these compounds. The solvent set of C6H6/CS2 gives 1:1:C6H6 compound 4 with unique charged anions, [CrIII(Cl4SQ)2(Cl4Cat)]-, while the other set, n-C6H12/CS2, affords 1:2 compound 6 including the two redox isomers, [CrIII(Cl4SQ)2(Cl4Cat)]- and [CrIII(Cl4SQ)3]0. The [CrIII(X4SQ)(X4Cat)2]2- anions in 1 and 2 show no significant interconnection between them (discrete type), while the [CrIII(X4SQ)2(X4Cat)]- anions in 4-6 show one-dimensional column-type structures with the aid of intermolecular stacking interactions of the ligand moieties. The anions in 4 show additional stacking interaction with the [FeIIICp2]+ to form one-dimensional ...[D][A][S][D][A]... (D = [FeIIICp2]+, A = [CrIII(Cl4SQ)2(Cl4Cat)]-, and S = C6H6) type mixed-stack arrangements similar to that of previously reported (CoIIICp2)[CrIII(Cl4SQ)2(Cl4Cat)].C6H6 (3). Compound 6 forms a two-dimensional sheet structure where the two redox isomers, [CrIII(Cl4SQ)2(Cl4Cat)]- and [CrIII(Cl4SQ)3]0, are included. The sheet is regarded as a mixed-valence molecular assembly. Two types of the anions, [CrIII(X4SQ)(X4Cat)2]2- (1 and 2) and [CrIII(X4SQ)2(X4Cat)]- (4-6), exhibiting an intramolecular mixed-valence state, show intramolecular intervalence CT transition (IVCT) from the Cat to the SQ at near 5800 and 4300 cm-1, respectively, both in the solution and in the solid states. The intermolecular mixed-valence state of 6 was characterized by absorption spectroscopy, electric conductivity, and SQUID magnetometry. Interestingly, this mixed-valence state of the chromium module is dependent on the redox active nature of the coordinated ligands.     

Synthesis, structure and solution NMR properties of (Ph4P)[M(SeC[O]Tol)3], M = Zn, Cd and Hg

Metal selenocarboxylate salts (PPh4)[M(SeC[O]Tol)3] (M = Zn (1), Cd (2) and Hg (3); Tol = C6H4-p-CH3) have been synthesized by reacting Zn(NO3)2 .6H2O, Cd(NO3)2 .4H2O or HgCl2 with (Na+)TolC[O]Se- and PPh4Cl in the ratio of 1 : 4 : 1. The structures of these compounds were determined by single-crystal X-ray diffraction methods. The crystal structures contain discrete cations and anions. In the each anion, the metal center is bound to three TolC[O]Se ligands, primarily through Se, though some long M...O interactions also occur. NMR spectra (113Cd, 199Hg and 77Se, as appropriate) are reported for solutions of [M(SeC[O]Tol)3]-, and of [M(SeC[O]Tol)3](-) - [M(SC[O]Ph)3]- mixtures (M = Zn-Hg), in CH2Cl2 at reduced temperatures. In addition, ESI-MS data have been obtained for [M(SeC[O]Tol)(3)](-) - [M(SC[O]Ph)3]- mixtures (M = Zn-Hg) in acetone and in CH2Cl2. The NMR and ESI-MS studies show that the complexes [M(SeC[O]Tol)n(SC[O]Ph)(3-n)]- (n= 3-0) persist in solution.     

Iron-arylimide clusters [Fe(m)()(NAr)(n)Cl(4)](2)(-) (m,n = 2, 2; 3, 4; 4, 4) from a ferric amide precursor: synthesis,characterization, and comparison to Fe-S chemistry

Tetrahedral FeCl[N(SiMe(3))(2)](2)(THF) (2), prepared from FeCl(3) and 2 equiv of Na[N(SiMe(3))(2)] in THF, is a useful ferric starting material for the synthesis of weak-field iron-imide (Fe-NR) clusters. Protonolysis of 2 with aniline yields azobenzene and [Fe(2)(mu-Cl)(3)(THF)(6)](2)[Fe(3)(mu-NPh)(4)Cl(4)] (3), a salt composed of two diferrous monocations and a trinuclear dianion with a formal 2 Fe(III)/1 Fe(IV) oxidation state. Treatment of 2 with LiCl, which gives the adduct [FeCl(2)(N(SiMe(3))(2))(2)](-) (isolated as the [Li(TMEDA)(2)](+) salt), suppresses arylamine oxidation/iron reduction chemistry during protonolysis. Thus, under appropriate conditions, the reaction of 1:1 2/LiCl with arylamine provides a practical route to the following Fe-NR clusters: [Li(2)(THF)(7)][Fe(3)(mu-NPh)(4)Cl(4)] (5a), which contains the same Fe-NR cluster found in 3; [Li(THF)(4)](2)[Fe(3)(mu-N-p-Tol)(4)Cl(4)] (5b); [Li(DME)(3)](2)[Fe(2)(mu-NPh)(2)Cl(4)] (6a); [Li(2)(THF)(7)][Fe(2)(mu-NMes)(2)Cl(4)] (6c). [Li(DME)(3)](2)[Fe(4)(mu(3)-NPh)(4)Cl(4)] (7), a trace product in the synthesis of 5a and 6a, forms readily as the sole Fe-NR complex upon reduction of these lower nuclearity clusters. Products were characterized by X-ray crystallographic analysis, by electronic absorption, (1)H NMR, and M?ssbauer spectroscopies, and by cyclic voltammetry. The structures of the Fe-NR complexes derive from tetrahedral iron centers, edge-fused by imide bridges into linear arrays (5a,b; 6a,c) or the condensed heterocubane geometry (7), and are homologous to fundamental iron-sulfur (Fe-S) cluster motifs. The analogy to Fe-S chemistry also encompasses parallels between Fe-mediated redox transformations of nitrogen and sulfur ligands and reductive core conversions of linear dinuclear and trinuclear clusters to heterocubane species and is reinforced by other recent examples of iron- and cobalt-imide cluster chemistry. The correspondence of nitrogen and sulfur chemistry at iron is intriguing in the context of speculative Fe-mediated mechanisms for biological nitrogen fixation.     

The first acetimino complexes of Rh(III). 4-imino-2-methylpentan-2-amino-Rh(III) complexes through metal-assisted intramolecular aldol-type condensation of two acetimino ligands

[Rh(Cp)Cl(mu-Cl)](2) (Cp = pentamethylcyclopentadienyl) reacts (i) with [Au(NH=CMe(2))(PPh(3))]ClO(4) (1:2) to give [Rh(Cp)(mu-Cl)(NH=CMe(2))](2)(ClO(4))(2) (1), which in turn reacts with PPh(3) (1:2) to give [Rh(Cp)Cl(NH=CMe(2))(PPh(3))]ClO(4) (2), and (ii) with [Ag(NH=CMe(2))(2)]ClO(4) (1:2 or 1:4) to give [Rh(Cp)Cl(NH=CMe(2))(2)]ClO(4) (3) or [Rh(Cp)(NH=CMe(2))(3)](ClO(4))(2).H(2)O (4.H(2)O), respectively. Complex 3 reacts (i) with XyNC (1:1, Xy = 2,6-dimethylphenyl) to give [Rh(Cp)Cl(NH=CMe(2))(CNXy)]ClO(4) (5), (ii) with Tl(acac) (1:1, acacH = acetylacetone) or with [Au(acac)(PPh(3))] (1:1) to give [Rh(Cp)(acac)(NH=CMe(2))]ClO(4) (6), (iii) with [Ag(NH=CMe(2))(2)]ClO(4) (1:1) to give 4, and (iv) with (PPN)Cl (1:1, PPN = Ph(3)P=N=PPh(3)) to give [Rh(Cp)Cl(imam)]Cl (7.Cl), which contains the imam ligand (N,N-NH=C(Me)CH(2)C(Me)(2)NH(2) = 4-imino-2-methylpentan-2-amino) that results from the intramolecular aldol-type condensation of the two acetimino ligands. The homologous perchlorate salt (7.ClO(4)) can be prepared from 7.Cl and AgClO(4) (1:1), by treating 3 with a catalytic amount of Ph(2)C=NH, in an atmosphere of CO, or by reacting 4with (PPN)Cl (1:1). The reactions of 7.ClO(4) with AgClO(4) and PTo(3) (1:1:1, To = C(6)H(4)Me-4) or XyNC (1:1:1) give [Rh(Cp)(imam)(PTo(3))](ClO(4))(2).H(2)O (8) or [Rh(Cp)(imam)(CNXy)](ClO(4))(2) (9), respectively. The crystal structures of 3 and 7.Cl have been determined.     

Syntheses and reactions of the fluorinated cyclic thionylphosphazene NSO(Ar)[NPF(2)]2(Ar = 4-t-BuC(6)H(4)-) with difunctional reagents

The S-aryl substituted thionylphosphazene (Cl(2)PN)(2)[4-t-BuC(6)H(4)(O)SN] (1) was prepared by Friedel-Craft's reaction of NSOCl(NPCl(2))(2) with tert-butylbenzene. When it reacted with excess KSO(2)F at 110 degrees C, the P-Cl bonds of 1 were fluorinated, yielding the tetrafluorothionylphosphazene, (F(2)PN)(2)[4-t-BuC(6)H(4)(O)SN] (2). An equimolar reaction of 2 with dilithiated 1,3-propanediol in THF at -78 degrees C resulted in the formation of the ansa-substituted compound CH(2)(CH(2)O)(2)[FPN](2)[4-t-BuC(6)H(4)(O)SN] (3). The crystal structures of 2 and 3 were determined. In 3 the ansa ring is trans on the PNS heterocycle with respect to the aryl group. Reaction of 2 with the disiloxane (CF(2)CH(2)OSiMe(3))(2), in the presence of catalytic amounts of CsF in THF at 90 degrees C, resulted in the formation of the dispiro compound [(CF(2)CH(2)O)(2)PN](2)[4-t-BuC(6)H(4)(O)SN] (4). Compounds 1-4 were characterized by IR, NMR ((1)H, (13)C, (19)F, (31)P), mass spectral, and elemental analyses.     

Structural diversity of lithium sulfenamides: 7Li NMR studies in solution and crystal structures of [Li2(eta2-(CH3)3C-NS-C6H4CH(3)-4)2(THF)2] and [Li2(eta1-4-CH3C6H4-NS-C6H4CH(3)-4)2(THF)4

Two lithium sulfenamides were prepared by reaction of (CH(3))(3)C-N(H)-S-C(6)H(4)CH(3)-4 (1) and 4-CH(3)C(6)H(4)-N(H)-S-C(6)H(4)CH(3)-4 (2) with an alkyllithium. The unsolvated sulfenamide Li[(CH(3))(3)C-NS-C(6)H(4)CH(3)-4] (3) was soluble enough for variable-temperature (VT) (7)Li NMR to provide evidence of a dynamic exchange of oligomers in solution. The crystal structures of the solvated sulfenamides of [Li(2)(eta(2)-(CH(3))(3)C-NS-C(6)H(4)CH(3)-4)(2)(THF)(2)] (4) and of [Li(2)(eta(1)-4-CH(3)C(6)H(4)-NS-C(6)H(4)CH(3)-4)(2)(THF)(4)] (6) consisted of dimers in which the anions display different hapticities. The VT (7)Li NMR spectra of 4 suggest that the two different structures exist in equilibrium in toluene-THF mixtures. These compounds are easily oxidized to the neutral thioaminyl radicals as identified by EPR spectroscopy.     

An unprecedented polyborate ester anion: X-ray diffraction studies on [1,8-C10H6(NMe2)2H][B5O6(OMe)4

The slow hydrolysis of B(OMe)3 in a CH2Cl2 solution in the presence of 1,8-C10H6(NMe2)2 (5:1 ratio) led to the formation of the novel isolated pentaborate ester anion [B5O6(OMe)4]-, which was characterized by a single-crystal X-ray diffraction study as the salt [1,8-C10H6(NMe2)2H][B5O6(OMe)4].     

Synthesis and structures of selected triazapentadienate of Li, Mn, Fe, Co, Ni, Cu(I), and Cu(II) using 2,4-N,N'-disubstituted 1,3,5-triazapentadienate anions as ancillary ligands: [N(Ar)C(NMe2)NC(NMe2)N(R)](-) (Ar = Ph, 2,6-(i)Pr2-C6H3; R = H, SiMe3)

Addition reaction of ArN(SiMe 3)M (Ar = Ph or 2,6 - (i) Pr 2-C 6H 3 (Dipp); M = Li or Na) to 2 equivalents of alpha-hydrogen-free nitrile RCN (R = dimethylamido) gave the dimeric [M{N(Ar)C(NMe 2)NC(NMe 2)N(SiMe 3)}] 2 ( 1a, Ar = Ph, M = Li; 1b, Ar = Ph, M = Na; 1c, Ar = Dipp, M = Li). 1d was obtained by hydrolysis of 1c at ambient temperature. Treatment of a double ratio of 1a or 1b with anhydrous MCl 2 (M = Mn, Fe, Co) yielded the 1,3,5-triazapentadienato complexes [M{N(Ph)C(NMe 2)NC(NMe 2)N(SiMe 3)} 2] (M = Mn, 2; Fe, 3; Co, 4) and with NiCl 2.6H 2O gave [M{N(Ph)C(NMe 2)NC(NMe 2)N(H)} 2] (M = Ni, 5). Treatment of an equiv of 1c with anhydrous CuCl in situ and in air led to complexes [{N(Dipp)C(NMe 2)NC(NMe 2)N(SiMe 3)}CuPPh 3] 6 and [Cu{N(Dipp)C(NMe 2)NC(NMe 2)N(H)} 2] 7, respectively. 1c, 1d, and 2- 7 were characterized by X-ray crystallography and microanalysis. 1c, 1d, 5, and 6 were well characterized by (1)H, (13)C NMR, 1c by (7)Li, and 6 by (31)P NMR as well. The structural features of these complexes were described in detail.     

Synthesis and spectroscopy of N3P3X5OCH=CH2 (X = Cl, F, OCH3, OCH2CF3, N(CH3)2) and N3P3X4(OCH=CH2)2 (X = Cl, N(CH3)2). Correlations of ultraviolet photoelectron spectroscopy and nuclear magnetic resonance data to electronic and geometrical structure

The syntheses of the vinyloxycyclotriphosphazene derivatives N3P3X5OCH=CH2 (X = OMe, OCH2CF3) and the N3P3(NMe2)4(OCH=CH2)2 isomeric mixture along with improved preparations of N3P3X5OCH=CH2 (X = F, NMe2) are reported. The interactions between the vinyloxy function and the cyclophosphazene in these and the previously reported N3P3Cl5 (OCH=CH2) and N3P3F6-n(OCH=CH2)n (n = 1-4) have been examined by ultraviolet photoelectron spectroscopy (UPS) and NMR spectroscopy. The UPS data for the chloro and fluoro derivatives show a strong electron-withdrawing effect of the phosphazene on the olefin that is mediated with decreasing halogen substitution. The 1H and 13C NMR data for N3P3X5OCH=CH2 (X = F, Cl, OMe, OCH2CF3, NMe2) show significant changes as a function of the phosphazene substituent. There is a linear correlation between the beta-carbon chemical shift on the vinyloxy unit and the phosphorus chemical shift at the vinyloxyphosphorus centers. The chemical shifts of the different phosphorus centers on each ring are also related in a linear fashion. These relationships may be understood in terms of the relative electron donor-acceptor abilities of the substituents on the phosphazene ring. The 1H NMR spectra of the N3P3(NMe2)4(OCH-CH2)2 isomeric mixture allow for assignment of the relative amounts of cis and trans isomers. A model for the observed cis preference in the formation of N3P3Cl4(OCH=CH)2 is presented.     

Different transmetallation behaviour of [M(P4HR4)] salts toward rhodium(I) and copper(I) (M = Na, K; R = Ph, Mes; Mes = 2,4,6-Me3C6H2)

[K(2)(P(4)Mes(4))] (1) or [Na(2)(THF)(4)(P(4)Mes(4))] (2) (Mes = 2,4,6-Me(3)C(6)H(2)) reacts with one equivalent of HCl and subsequently with 0.5 equivalents of [{RhCl(cod)}(2)] (cod = 1,5-cyclooctadiene) to give a mixture of rhodium complexes, from which [Rh(P(4)HMes(4))(cod)] (3) and the secondary product [Rh(2)(micro-P(2)HMes(2))(mu-PHMes)(cod)(2)] (4) were isolated and characterised by X-ray diffraction studies. Alternatively, the reaction of [K(2)(P(4)Ph(4))] (5) or [Na(2)(THF)(5)(P(4)Ph(4))] (6) with one equivalent of HCl and subsequently with one equivalent of [CuCl(PCyp(3))(2)] (Cyp = cyclo-C(5)H(9)) gave the complex [Cu(4)(P(4)Ph(4))(2)(PH(2)Ph)(2)(PCyp(3))(2)] (7), presumably via disproportionation of the monoanion (P(4)HPh(4))(-).