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tBu2P-P(SiMe3)Li reacted with [(η6-C6H6)RuCl2]2 at -40 °C in the presence of PR3 (PR3 = PEt3, PEt2Ph, PEtPh2) by the nucleophilic addition of the tBu2P-P(SiMe3) moiety to the benzene ring to yield solely the complexes [(R3P)2Ru(Cl){η5-C6H6(Me3SiP-P tBu2)}] ( 1). These products decomposed slowly at ambient temperature to yield benzene, Ru clusters, and small amounts of the dinuclear ruthenium complexes [{(R3P)2Ru}2(µ,η2:2-P2)2Ru(PR3)2] ( Ru-Ru) ( 6). Single-crystal X-ray diffraction studies of [(PhEt2P)2Ru(Cl){η5-C6H6(Me3SiP-P tBu2)}] ( 1b) and [(Ph2EtP)2Ru(Cl){η5-C6H6(Me3SiP-P tBu2)}] ( 1c) revealed that the addition of the tBu2P-P(SiMe3) group occurred through an exo pathway. Complex 6a (R = Et) displays a planar rectangular P4 system consisting of two P2 units and a Ru-Ru distance that lies in the range of a single bond. [ABSTRACT FROM AUTHOR]

The nucleophilic properties of the title compound [(2,6-i-Pr2C6H3N)2(Cl)W(η2-t-Bu2P=P)]Li·3DME (1) were investigated in reactions with selected electrophilic reagents such as MeI, M(CO)5THF (M = Cr, Mo, W), AlCl3, and GaCl3. Methylation of 1 by MeI yields phosphanylphosphido complexes [(2,6-i-Pr2C6H3N)2W(X)(1,2-η-t-Bu2P=P–CH3)] (X = Cl, I) (2-Cl/2-I) with the formation of a new P–C bond. Moreover, 1 reacts with electrophilic compounds [(OC)5M·THF] (M = Cr, Mo, W) to yield a series of novel dinuclear phosphanylphosphinidene complexes [(2,6-i-Pr2C6H3N)2(Cl)W(1,2-η-t-Bu2P=P–M(CO)5)]Li·3DME (3, 4, 5) with very long P–M distances. Adducts [(2,6-i-Pr2C6H3N)2(Cl)W(1,2-η-t-Bu2P=P–MCl3)]Li·3DME (6, 7) formed by reaction of 1 with GaCl3 and AlCl3 are labile and dissociate into 1 and MCl3 (M = Ga, Al). The outcomes of reactions were monitored by 31P-NMR spectroscopy. Furthermore, the structures of the isolated complexes 2-Cl/2-I, 3, 4, and [(2,6-i-Pr2C6H3N)2(Cl)W(1,2-η-t-Bu2P=P–W(t-Bu2PH)(CO)3COLi·2DME] (5-P) were confirmed unambiguously by X-ray diffraction studies. [ABSTRACT FROM AUTHOR]

The reaction of R2P-P(SiMe3)Li (R = tBu, iPr) with the diimido molybdenum complex [(ArN)2MoCl2 ·dme] (Ar = 2,6- iPr2C6H3; dme = 1,2-dimethoxyethane) yielded the side-on-coordinated phosphanylphosphinidene anionic complexes [(2,6- iPr2C6H3N)2Mo(Cl)(η2-P=PR2)]- ( 7Mo, 8Mo). The thermal decomposition of [(2,6- iPr2C6H3N)2M(Cl)(η2-P=PR2)]- [M = Mo ( 7Mo), W ( 8W)] to [(2,6- iPr2C6H3N)2M(Cl)(1,2-η- tBu2P=P-P tBu2)] [M = Mo ( 3Mo), W ( 3W)] was investigated by 31P{1H} NMR spectroscopy. The reactions of [(ArN)2MCl2 ·dme] (Ar = 2,6- iPr2C6H3; M = Mo, W) with tBu2P-P(Li)-P tBu2 gave molybdenum and tungsten complexes [(2,6- iPr2C6H3N)2M(Cl)(1,2-η- tBu2P=P-P tBu2)] ( 3Mo, 3W) bearing an unusual triphosphorus ligand. The solid-state structures of [(2,6- iPr2C6H3N)2Mo(Cl)(η2-P=P tBu2)]- ( 7Mo), [(2,6- iPr2C6H3N)2Mo(Cl)(η2-P=P iPr2)]- ( 8Mo), [(2,6- iPr2C6H3N)2Mo(Cl)(1,2-η- tBu2P=P-P tBu2)] ( 3Mo) and [(2,6- iPr2C6H3N)2W(Cl)(1,2-η- tBu2P=P-P tBu2)] ( 3W) were established by single-crystal X-ray diffraction analysis. [ABSTRACT FROM AUTHOR]

Manganese(III)-promoted cyclization of N-alkenylmalonamides (= N-alkenylpropanediamides) gave 3-(aryl/(alkylamino)carbonyl) β-lactams as well as 3-(aryl/(alkylamino)thiocarbonyl) β-lactams. The relative configuration of the obtained products was unambiguously determined by X-ray crystallography. The proposed method is very useful for the one-pot synthesis of a number of 3-(aryl/(alkylamino)carbonyl) β-lactams, especially those containing an amino(thiocarbonyl) moiety, which are not selectively accessible by other methods. [ABSTRACT FROM AUTHOR]

The title complex, neutral {[Ni2(μ-S2O3)2(C7H9N)4H2O]C7H8} ( 1), presents a dinuclear structure with the thiosulfate group acting as a (S, O) chelate and simultaneously as a (S) bridge. The molecular structure was determined by X-ray crystallography. Complex 1 crystallizes as a hydrogen-bonded dimer with molecule of toluene solvent in the unit cell. The environment of both central nickel atoms is octahedral with NiN2O2S2 cores. This is the first metal thiosulfate complex isolated as a product of the oxidation of silanethiol. A mechanism of the reaction involving the formation of ( RO)3SiSSSi(O R)3 intermediate is proposed with the subsequent cleavage of Si-S bond. [ABSTRACT FROM AUTHOR]

The title complex, neutral {[Ni2(μ-S2O3)2(C7H9N)4H2O]C7H8} ( 1), presents a dinuclear structure with the thiosulfate group acting as a (S, O) chelate and simultaneously as a (S) bridge. The molecular structure was determined by X-ray crystallography. Complex 1 crystallizes as a hydrogen-bonded dimer with molecule of toluene solvent in the unit cell. The environment of both central nickel atoms is octahedral with NiN2O2S2 cores. This is the first metal thiosulfate complex isolated as a product of the oxidation of silanethiol. A mechanism of the reaction involving the formation of ( RO)3SiSSSi(O R)3 intermediate is proposed with the subsequent cleavage of Si-S bond. [ABSTRACT FROM AUTHOR]

Abstract: Dichloro-bis(indenyl)zirconium(IV) reacts with lithium derivatives of diphosphanes R2P–P(SiMe3)Li (R= tBu, Et2N, iPr2N) to form complexes with terminal phosphanylphosphido ligands – [Ind2Zr(Cl)-{(PSiMe3)P-PR2-κP1}]. These compounds are extremely sensitive towards moisture and oxygen. The solid state structures of these complexes were established by single crystal X-ray diffraction. The nitrogen bearing groups R (Et2N or iPr2N) significantly lengthen the P–P distances in the related complexes and change the geometry around the phosphido phosphorus in such a way that it becomes less planar. [Copyright &y& Elsevier]

This study was focused on the activation of the CP bond via reactions of Ph 2 CP-P t Bu 2 (1) with 1,6-hexanediol and selected dithiols (1,4-butanedithiol, 1,4-benzenedithiol and 1,4-benzenedimethanethiol). These reactions proceed according to a 1,2-addition mechanism, providing new compounds with formulas {(Ph) 2 (H)C-P-P t Bu 2 }{μ 2 -(O-(CH 2 ) 6 -O)}{ t Bu 2 P-P-C(H)(Ph) 2 } (2), {(Ph) 2 (H)C-P-P t Bu 2 }{μ 2 -(S-(CH 2 ) 4 -S)}{ t Bu 2 P-P-C(H)(Ph) 2 } (3a), {(Ph) 2 (H)C-P-P t Bu 2 }{μ 2 -(S-C 6 H 4 -S)}{ t Bu 2 P-P-C(H)(Ph) 2 } (3b), and {(Ph) 2 (H)C-P-P t Bu 2 }{μ 2 -(S-CH 2 -C 6 H 4 -CH 2 -S)}{ t Bu 2 P-P-C(H)(Ph) 2 } (3c). Next, the reactions of 3a and 3c with metal chlorides led to the growth of desired coordination polymers of copper(I) and silver(I). All the obtained compounds remained stable under atmospheric conditions.

Three reactions of phosphanylphosphaalkene (1) with nucleophiles were performed to activate the diphosphorus monomer. We observed similar results in the reactions with MeLi and n BuLi, in which the P-P bond is cleavaged and triphosphorus systems [P(Me) 2 -CH(biph)-CH(biph)-P-(P t Bu 2 )] - (1a'') and [P( n Bu) 2 -CH(biph)-CH(biph)-P-(P t Bu 2 )] - (1b''), respectively, are formed depending on the nucleophilic reagent (biph = biphenyl). In the case of t BuLi, the P-P bond remains intact; on the phosphorus atom, only one - t Bu group is substituted, and as a result, [(biph)(H)C-P( t Bu)-P t Bu 2 ] - (1c) is generated as a stable carbanion. We additionally investigated the effect of substitution in the phenyl ring in the course of these reactions by involving two other phosphanylphosphaalkenes (3 and 4). All initial reactions were conducted in tetrahydrofuran (THF) solution at ambient temperature., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

In this work, we report a new type of reactivity of [(BDI*)Ti(Cl){η2-P(SiMe3)-PiPr2}] (1) towards ketones (BDI* = 2,6-diisopropylphenyl-β-methyldiketiminate ligand). In the reaction of 1 with acetone, cyclopentanone or cyclohexanone, a ketone moiety is inserted into Ti-Pphosphanyl or Ti-Pphosphido bonds to form complexes with a new C-P-P moiety, providing [(BDI*)Ti(Cl){η2-P(SiMe3)-PiPr2-C(Me)2O}] (2a), [(BDI*)Ti(Cl){η2-OC(Me)2P(SiMe3)-PiPr2}] (2b), [(BDI*)Ti(Cl){η2-P(SiMe3)-P(iPr)2-{C(CH2)4}O}] (3a), and [(BDI*)Ti(Cl){η2-P(SiMe3)-P(iPr)2-{C(CH2)5}O}] (4a). Starting complex 1 reacts with cyclohexanone, yielding a monocrystalline complex [{(ArN[double bond, length as m-dash]C(Me)CHC(Me)[double bond, length as m-dash]NAr)C(CH2)5O}Ti(Cl){PiPr2-P(SiMe3)C(CH2)5O}] (4d) with the insertion of two ketone molecules. Interestingly, we found that monoinserted complexes 2a and 3a may be oxidized via a reaction with AgCl, leading to elimination of the -SiMe3 group and oxidation of the titanium atom. This reaction led us to isolate the Ti(iv) complex [(BDI*)Ti(Cl){η2-P-P(iPr)2-{C(CH2)5}O}] (5) in crystalline form. To identify the kinds of products that may be formed and determine which products are the most energetically favoured ones, we conducted a thermodynamic DFT study of 1 towards acetone, cyclopentanone and cyclohexanone. Structures 2a, 2b, 3a, 3e, 4a, 4d, and 5 were characterized by X-ray crystallography, and complex 5 was also identified by NMR spectroscopy.

A reactivity study of a β-diketiminate titanium(iii) phosphanylphosphido complex [ Me NacNacTi(Cl){η 2 -P(SiMe 3 )-PtBu 2 }] (1) towards ketones such as benzophenone, 9-fluorenone, acetophenone, cyclopentanone, cyclohexanone and cycloheptanone is reported. The reactions of 1 with aromatic ketones (without α-protons) directly lead to the Ti(iii) complex [ Me NacNacTi(μ 2 -Cl)(OSiMe 3 )] (5) and Ti(iv) complexes with the pinacol condensation product [ Me NacNacTi(OSiMe 3 )(η 2 -pinacolate)] (3), and phosphanylphosphaalkenes Ph 2 C[double bond, length as m-dash]P-PtBu 2 (2) and (fluorenyl)C[double bond, length as m-dash]P-PtBu 2 (6), respectively. The reaction with acetophenone leads to the titanium(iii) complex with the aldol condensation product as ligand [ Me NacNacTi(Cl){OC{Me(Ph)}CH 2 (C[double bond, length as m-dash]O)Ph}] (8) and in parallel to phosphanylphosphaalkene (Ph)MeC[double bond, length as m-dash]P-PtBu 2 (9) and 5. The reactions of 1 with cyclic ketones (cyclopentanone and cyclohexanone) lead to Ti(iii) complexes [{(ArN[double bond, length as m-dash]C(Me)CHC(Me)[double bond, length as m-dash]NAr)((CH 2 ) 4 CO)}Ti(Cl){PtBu 2 -P(SiMe 3 )((CH 2 ) 4 CO)}] (10) and [{(ArN[double bond, length as m-dash]C(Me)CHC(Me)[double bond, length as m-dash]NAr)((CH 2 ) 5 CO)}Ti(Cl){PtBu 2 -P(SiMe 3 )((CH 2 ) 5 CO)}] (11), which are formed via the successive insertion of two molecules of ketone to one molecule of 1. The stability investigation of complexes 10 and 11 in a polar solvent (THF) revealed that under these conditions, the complexes decompose, resulting in titanium(iii) complexes with aldol condensation products and the expected phosphanylphosphaalkenes (CH 2 ) 4 C[double bond, length as m-dash]P-PtBu 2 (10a) and (CH 2 ) 5 C[double bond, length as m-dash]P-PtBu 2 (11a). In the reaction of 1 with cycloheptanone, only the Ti(iii) complex with the aldol condensation product [ Me NacNacTi(Cl){OC(CH 2 ) 6 }CH(C[double bond, length as m-dash]O)(CH 2 ) 5 ] (12) was isolated. The structures 3, 5, 8, 10, 11, 11b and 12 were characterized by X-ray spectroscopy, while all the phosphanylphosphaalkenes were characterized by NMR spectroscopy.

The first example of CO2 diphosphination is described. Reactions of unsymmetrical diphosphanes with CE2 (E = O, S) catalyzed by BPh3 insert a CE2 molecule into the P-P bond with formation of the products of the general formula R2P-E-C([double bond, length as m-dash]E)-PR2. The obtained CO2 adducts arise from synergistic interaction of diphosphane and borane with CO2 molecule.

Herein, the lithium derivative of diphosphane, (Ph)tBuP-P(SiMe3)Li (1), is isolated for the first time and investigated in reactions with β-diketiminate (MeNacnac- = [Ar]NC(Me)CHC(Me)N[Ar]; Ar = 2,6-iPr2C6H3) and PNP-pincer (PNP = N[2-PiPr2-4-methylphenyl]2) Ti(iii) complexes. The β-diketiminate titanium(iii) complex containing the phosphanylphosphido ligand [MeNacNacTi(Cl){η2-P(SiMe3)-P(Ph)tBu}] (2) is prepared via the reaction of [MeNacNacTiCl2·THF] with (Ph)tBuP-P(SiMe3)Li in toluene solution with good yield and purity. The corresponding titanium(iv) complex involving the phosphanylphosphinidene ligand [MeNacNacTi(Cl){η2-P-P(Ph)tBu}] (3) is synthesized via the oxidation of complex (2) with [iBu3PAgCl]4. Interestingly, an analogous PNP titanium(iv) complex, [(PNP)Ti(Cl){η2-P-P(Ph)tBu}] (4), is obtained in the reaction of [(PNP)TiCl2] with (Ph)tBuP-P(SiMe3)Li in toluene solution and a 1 : 1 molar ratio instead of the expected titanium(iii) complex with the phosphanylphosphido ligand. The solid-state structures of (Ph)tBuP-P(SiMe3)Li·3THF (1), [MeNacNacTi(Cl){η2-P(SiMe3)-P(Ph)tBu}] (2), [MeNacNacTi(Cl){η2-P-P(Ph)tBu}] (3) and [(PNP)Ti(Cl){η2-P-P(Ph)tBu}] (4) are determined by single-crystal X-ray diffraction, which reveals that in all obtained complexes, both the phosphanylphosphinidene (Ph)tBuP-P and phosphanylphosphido (Ph)tBuP-P(SiMe3) ligands are bidentate-coordinated to the metal center.

The nucleophilic properties of the title compound [(2,6-i-Pr2C6H3N)2(Cl)W(η(2)-t-Bu2P = P)]Li·3DME (1) were investigated in reactions with selected electrophilic reagents such as MeI, M(CO)5THF (M = Cr, Mo, W), AlCl3, and GaCl3. Methylation of 1 by MeI yields phosphanylphosphido complexes [(2,6-i-Pr2C6H3N)2W(X)(1,2-η-t-Bu2P = P-CH3)] (X = Cl, I) (2-Cl/2-I) with the formation of a new P-C bond. Moreover, 1 reacts with electrophilic compounds [(OC)5M·THF] (M = Cr, Mo, W) to yield a series of novel dinuclear phosphanylphosphinidene complexes [(2,6-i-Pr2C6H3N)2(Cl)W(1,2-η-t-Bu2P = P-M(CO)5)]Li·3DME (3, 4, 5) with very long P-M distances. Adducts [(2,6-i-Pr2C6H3N)2(Cl)W(1,2-η-t-Bu2P = P-MCl3)]Li·3DME (6, 7) formed by reaction of 1 with GaCl3 and AlCl3 are labile and dissociate into 1 and MCl3 (M = Ga, Al). The outcomes of reactions were monitored by (31)P-NMR spectroscopy. Furthermore, the structures of the isolated complexes 2-Cl/2-I, 3, 4, and [(2,6-i-Pr2C6H3N)2(Cl)W(1,2-η-t-Bu2P = P-W(t-Bu2PH)(CO)3COLi·2DME] (5-P) were confirmed unambiguously by X-ray diffraction studies.

Self-assembled bi- and polymetallic complexes of Co(II), Ni(II), Zn(II), and Cd(II) were obtained by the reaction of 4,4'-azopyridine (azpy) with metal tri-tert-butoxysilanethiolates (Co, 1; Cd, 2), acetylacetonates (Ni, 3; Zn, 4), and acetates (Cd, 5). All compounds were characterized by single-crystal X-ray structure analysis, elemental analysis, FTIR spectroscopy, and thermogravimetry. Complexes 1, 2 and 4, 5 exhibit diverse structural conformations: 1 is bimetallic, 2 and 4 are 1D coordination polymers, and 5 is a 2D coordination framework formed from bimetallic units. The obtained complexes contain metal atoms bridged by a molecule of azpy. The luminescent properties of 1-5 were investigated in the solid state., (© 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)