Organoimido Ligand Research Articles

A Heteroaromatically Functionalized Hexamolybdate

A new heteroaromatic thiophene containing organoimido functionalized hexamolybdate has been synthesized and characterized in both solid form and solution. Structural analysis shows successful introduction of the organoimido ligand through replacement of one terminal oxo site on [Mo6O19]2− to yield the singly functionalized hexamolybdate. Spectroscopic and theoretical analysis indicates charge transfer between the inorganic and organic components, with a significantly red-shifted lowest lying transition of 399 nm vs. the parent Lindqvist ion of 325 nm. Additional characterization includes, thermal gravimetric analysis (TGA), infrared (IR), cyclic voltammetry (CV), nuclear magnetic resonance (NMR) and time-dependent density functional theory (TD-DFT) studies.

Aliphatic organoimido derivatives of polyoxometalates containing a bioactive ligand.

A series of aliphatic organoimido derivatives of hexamolybdate based on amantadine, namely (nBu4 N)2 [Mo6 O18 (NC10 H15 )] (1), (nBu4 N)2 {cis-[Mo6 O17 (NC10 H15 )2 ]} (2), (nBu4 N)2 {trans-[Mo6 O17 (NC10 H15 )2 ]} (3), and (nBu4 N)2 [Mo6 O16 (NC10 H15 )3 ] (4), was synthesized in reasonable yield by dehydration with N,N'-dicyclohexylcarbodiimide (DCC). They were characterized by IR and UV/Vis spectroscopy, elemental analysis, ESI mass spectrometry, and single-crystal X-ray structure analysis. The spectral and structural similarities and differences between monosubstituted, cis-disubstituted, and trans-disubstituted organoimido derivatives were elucidated and may provide guidance for related work on organoimido-functionalized Lindqvist-type polyoxometalates. In addition, trans-disubstituted and polysubstituted derivatives containing aliphatic organoimido ligands have not yet been reported, and the crystal structure of the trans isomer may lead us to a deeper understanding of disubstituted derivatives. Furthermore, proliferation and morphology of MCF-7 cells were studied with compound 1. The present results show that the DCC-dehydrating protocol could be an efficient approach to covalently graft bioactive ligands such as amantadine onto POMs and enhance their application in clinical cancer treatment.

A DFT Study on The Two‐Dimensional Second‐Order Nonlinear Optical (NLO) Response of Terpyridine‐Substituted Hexamolybdates: Physical Insight on 2D Inorganic–Organic Hybrid Functional Materials

AbstractDFT calculations were carried out in order to study the second‐order nonlinear optical (NLO) response of a series of proposed 2D polyoxometalate‐based terpyridine‐substituted compounds. These compounds can be formulated as [Mo6O17{N4C25H16(X)2}{N4C25H16(X)2}]2– (X = H, F, Cl, Br, I, CF3, or CN), which has a wedge Λ‐shaped acceptor––π‐conjugated bridge––donor––π‐conjugated bridge––acceptor (A‐π‐D‐π‐A) configuration. The calculations showed that these compounds possess significantly large molecular second‐order polarizabilities that range from approximately 1000 × 10–30 to 4300 × 10–30 esu. The combination of trifluoromethyl (CF3) and cyanide (CN) groups at the end of the terpyridine ligand strengthens the bridge conjugation, which is useful for the enhancement of the NLO response. In addition, the greatest contributions to the βvec values are dervied from the charge transfer (CT) from the Mo≡N bond and the organoimido ligand to the terpyridine‐substituted segments. This report demonstrates that various combinations of the acceptor(s) remarkably affect the second‐order NLO response. The electronic transitions to the crucial excited states indicated that the y polarized transition contributed to the off‐diagonal second‐order polarizabiliy tensor (βzyy) and that the z polarized transition accounted for the diagonal second‐order polarizabiliy tensor (βzzz). Thus, itsteered towards in‐plane nonlinear anisotropy (u = βzyy/βzzz) along with a good 2D second‐order NLO response. These compounds can be used as good 2D second‐order NLO materials from the point of view of their large β values.

Electronic Properties of Unprecedented Bridging Organoimido-Substituted Hexamolybdate: New Insights from Density Functional Theory Study

The organoimido functionalization of polyoxometalates (POMs) has drawn tremendous attention due to particular merits in fabricating POM-based hybrid materials with finely tunable properties. The electronic properties, orbital and bonding characters of unprecedented bridging organoimido-substituted hexamolybdate are investigated using density functional theory methods. Among the organoimido-bridged hexamolybdates, [Mo(6)O(16)(2,6-Me(2)-NC(6)H(3))(2)(mu(2)-2,6-Me(2)-NC(6)H(3))](2-) (3-Ar-1), which features two terminal and one bridging organoimido ligand, is more favorable. The calculations confirm that the three-center (3c) pi bond originates from the coplanarity of bridging nitrogen atom with two Mo atoms and the hybridization of bridging nitrogen. The 3c bond stabilizes the organoimido-bridged anion 3-Ar-1. Compared with cis-bifunctionalized organoimido derivative [Mo(6)O(17)(2,6-Me(2)-NC(6)H(3))(2)](2-) (2-Ar), the bonding interaction between terminal organoimido ligand and hexamolybdate cluster in 3-Ar-1 is strengthened by the bridging organoimido. The results are in good agreement with the analysis of the Wiberg bond index of the Mo-N bond. The organoimido segment modifies the occupied molecular orbitals of organoimido hexamolybdates. The unoccupied molecular orbitals in 3-Ar-1 are largely nonbonding O(p) and Mo(d) orbitals in character, which resemble those of 2-Ar.

Tuning Second-Order Non-linear (NLO) Optical Response of Organoimido-Substituted Hexamolybdates through Halogens: Quantum Design of Novel Organic-Inorganic Hybrid NLO Materials

The second-order non-linear optical (NLO) response of organoimido-substituted hexamolybdates has been tuned from 218.61 × 10–30 to 490.10 × 10–30 esu. The dipole polarizabilities and second-order nonlinear optical (NLO) properties of organoimido derivatives of hexamolybdates have been investigated by using the time-dependent density functional response theory (TDDFT). The electron withdrawing ability of F (fluorine) has played an important role in tuning the second-order NLO response in this class of organic-inorganic hybrid compounds; particularly system 6 [Mo6O18(NC16H8F2(CF3)2I)]2– with the static second-order polarizability (βvec ) computed to be 490.10 × 10–30 esu. Thus, our studied systems have the feasibility to be excellent tuneable second-order NLO materials. The analysis of the major contributions to the βvec value suggests that the charge transfer (CT) from POM to organic ligand (D-A) along the z-axis has been enhanced with addition of F atoms at the end phenyl ring which directs head (POM) to tail (fluorinated ring) charge transfer. The computed βvec values have been tuned by incorporation of different halogen atoms at the end phenyl ring of organoimido segment. Furthermore, substitution of two trifluoromethyl (–CF3) groups sideways along with iodine (I) at the terminus of end phenyl ring in the organoimido ligand has a striking influence on tuning the optical non-linearity, as CT from POM to the organoimido ligand was significantly increased. These systematic small changes in molecular composition by substitution of different halogen groups leads to a tuning the NLO response; the so-called ‘ripple effect’ catches this point nicely. Thus, the present investigation provides thought provoking insight into the tuneable NLO properties of organoimido-substituted hexamolybdates.

Synthesis and characterization of the organoimidopolyoxomolybdates [ n -Bu4N]2[Mo6O17(≡NAr)2] (Ar = 2-ethyl-6-methylphenyl and 2-isopropyl-6-methylphenyl)

Two new bifunctionalized arylimido derivatives of hexamolybdate, [n-Bu4N]2[Mo6O17(C6H3N-2-C2H5-6-CH3)2] (1) and [n-Bu4N]2[Mo6O17(C6H3N-2-CH(CH3)2-6-CH3)2] · H2O (2), in which the two organoimido groups are covalently bonded to hexamolybdate at the cis positions, were synthesized by self-assembled metathesis of α-octamolybdate and organoimido ligands with N,N′-dicyclohexylcarbodiimide as dehydration agent, and characterized by elemental analysis, 1H NMR, IR and electronic spectroscopy, and X-ray diffraction analysis. Both derivatives have short Mo–N bond distances [Mo(1)–N(1), 1.740(3) Å; Mo(2)–N(2), 1.739(3) Å for 1 and Mo(1)–N(1), 1.734(3) Å; Mo(2)–N(2), 1.741(3) Å for 2] and form dimers via π–π stacking in the crystalline state.

Naphthyl Amines as Novel Organoimido Ligands for Design of POM-Based Organic−Inorganic Hybrids: Synthesis, Structural Characterization, and Supramolecular Assembly of (Bu4N)2[Mo6O18N(Naph-1)

A novel naphthylimido derivative of hexamolybdate, (Bu4N)2[Mo6O18N(Naph-1)] (1), was synthesized for the first time by the reaction of octamolybdate ion and 1-naphthyl amine hydrochloride with DCC (N,N‘-dicyclohexylcarbodiimide) as a dehydrating agent. The ultraviolet−visible absorption spectrum shows the lowest energy electronic transition of 1 occurs at 383 nm, which is dramatically red-shifted compared to that of [Mo6O19]2- and other monosubstituted phenylimido hexamolybdates reported in the literature. Moreover, cyclic voltammetry studies on compound 1 show the reversible reduction wave at −0.53 V, which is cathodically shifted relative to that of [Mo6O19]2-. Another interesting characteristic of 1 is that the cluster anions form supramolecular 1D chains via C−H···O hydrogen bonding interactions.

Transition Metal Complexes Containing Functionalized Organoimido and Phosphaneiminato Ligands

AbstractTwo different types of modified imido and phosphaneiminato ligands are investigated, namely chelate ligands and redox‐functionalised ligands. The first examples of di(organoimido)chromium as well as di(phosphaneiminato)titanium and niobium chelates are described. Furthermore, the first complexes containing redox‐functionalised organoimido ligands are presented, together with the first structurally characterised redox‐functionalised phosphaneiminato complex. Compounds of the type [(RN)2M(CH2Ph)2] (M = Cr, Mo) are used as catalysts for the (co‐)polymerisation of the polar olefins methyl methacrylate, acrylonitrile and vinyl acetate. A range of X‐ray crystal structure determinations provide clear evidence for the quantum‐chemical result that, similar to organoimido complexes, the potential energy well for the angle at the nitrogen atom is very shallow for phosphaneiminato complexes.

A New Class of Functionalized Polyoxometalates: Synthetic, Structural, Spectroscopic, and Electrochemical Studies of Organoimido Derivatives of [Mo6O19]2-

A convenient method for the systematic introduction of a variety of organoimido ligands at terminal oxo sites in the hexamolybdate cluster [Bu4N]2[Mo6O19] is described, consisting of reaction with the appropriate organic isocyanate RNCO (R = n-butyl, cyclohexyl, 2,6-diisopropylphenyl) in pyridine solution. Singly functionalized imido-hexamolybdates [Mo6O18(NR)]2- incorporating each of the above substituents are described. In the case of the 2,6-(diisopropyl)phenylimido ligand (NAr), multiple functionalization has also been achieved: hexamolybdate derivatives [Mo6O(19-x)(NAr)x]2- incorporating two, three, four, and five NAr ligands at terminal sites have been prepared. The complexes have been characterized by cyclic voltammetry, multinuclear (1H, 14N, 17O, and 95Mo) NMR and electronic spectroscopy, and single-crystal X-ray diffraction studies.

Synthesis, Structural Characterization, and MO Calculations of Vanadium Imido Complexes Containing Bidentate Phosphine Coligands.

Treatment of complex V(N-2,6-(i)Pr(2)C(6)H(3))Cl(3) with 1,2-dimethoxyethane (dme) gives in quasi-quantitative yield the adduct V(N-2,6-(i)Pr(2)C(6)H(3))Cl(3)(dme) (1). Interaction of 1 with bidentate phosphines gives V(N-2,6-(i)Pr(2)C(6)H(3))Cl(3)(P-P) (P-P = depe, 2a; dppe, 2b) compounds. An X-ray analysis (monoclinic, space group P2(1)/c, a = 14.7387(14) Å, b = 10.6738(10) Å, c = 16.999(3) Å, beta = 90.954(2) degrees, Z = 4, R = 0.0544), carried out on complex 2a, shows a mer arrangement of the chloride ligands and a nonsymmetrical coordination of the diphosphine ligand. One of the phosphorus atoms occupies the trans position with respect to the organoimido ligand. MO calculations on the models V(NR)Cl(3)(H(2)PCH(2)CH(2)PH(2)) (R = H, C(6)H(5)) of complex 2a were performed. The mer isomer, which is more stable than the fac isomer, shows good agreement with the experimental data.

Synthesis and characterization of d 2-molybdenum imido complexes containing coordinated dithio-ligands. MO rationalization of the preferential isomer formation of Mo(N-2,4,6-Me 3C 6H 2)(S 2COMe)Cl(PMe 3) 2

Treatment of the complex Mo(Nmes)Cl 2(PMe 3) 3 ( 1) (mes=2,4,6-Me 3C 6H 2, 2,4,6-trimethylphenyl) with two equivalents of the potassium salt of methyl xanthate, KS 2COMe, or the potassium 1-pyrrole-carbodithioate, KS 2C(NC 4H 4), gave Mo(Nmes)(S-S) 2(PMe 3) (S-S=S 2COMe 2; S 2C(NC 4H 4) 3). When the reaction of 1 with KS 2COMe is carried out in a 1:1 stoichiometry, the complex Mo(Nmes)(S 2COMe)Cl(PMe 3) 2 ( 4) is obtained. The chlorine atom in 4 occupies the trans position with respect to the organoimido ligand. MO calculations of the EH type rationalize the preferential formation of 4 as the thermodynamically preferred isomer in this metathesis reaction. The reaction of 4 with CO produces Mo(Nmes)(S 2COMe)Cl(CO)(PMe 3) ( 5). Reaction of 1 with carbon disulfide yields the complex Mo(Nmes)Cl 2(S 2CPMe 3) ( 6), containing a trihapto-( S, S′, C) phosphoniumdithiocarboxylate ligand.

Disruption of the π-perpendicular component of a 4-electron donor alkyne ligand in a high-valent complex of tungsten by introduction of an organoimido ligand

Addition of Me3SiNHCMe3 to the 4-electron donor alkyne complex [{WCl4(PhC2Ph)}2] gave [{WCl2(NCMe3)(PhC2Ph)(NH2CMe3)}x] 1 for which the acetylenic carbon resonance position, δ 156.23, in the 13C-{1H} NMR spectrum indicated a 2-electron donor alkyne. Small changes in δ for derivatives [NEt4][WCl3(NCMe3)(PhC2Ph)(NH2CMe3)] 2 (161.28), trans-dichloro complexes [WCl2(NCMe3)(PhC2Ph)(bipy)] 3 (bipy = 2,2′-bipyridyl, δ 163.60) and [WCl2(NCMe3)(PhC2Ph)(dmbipy)] 4 (dmbipy = 4, 4′-dimethyl-2,2′-bipyridyl, δ 162.93) as well as cis-dichloro complexes [WCl2(NCMe3)(PhC2Ph)(py)2] 5 (py = pyridine, δ 155.78), [WCl2(NCMe3)(PhC2Ph)(PMe3)2] 6 (δ 151.15) and [WCl2(NCMe3)(PhC2Ph)(PMe2Ph)2] 7 (δ 153.37) indicate small electronic differences in the alkyne–metal bonding. A crystal structure determination of 6 showed trans-phosphines, cis-chloro ligands and a cis arrangement of a 4-electron donor imido ligand [W–N 1.763(6) Å] and a 2-electron donor alkyne [W–C 2.131(6) and 2.111(7) Å]. The compound Me3SiNHCHMe2 added to [{WCl4(PhC2Ph)}2] followed by dmbipy gave [WCl2(NCHMe2)(PhC2Ph)(dmbipy)] 8 (δ 163.16), Me3SiNHCH2Me and dmbipy formed cis- and trans-dichloro complexes [WCl2(NCH2Me)(PhC2Ph)(dmbipy)] 9 (δ 152.76 and 159.03) and 10 (δ 163.31) respectively. A crystal structure of determination 10 showed W–C bond lengths [2.085(8) Å] somewhat shorter than in 6, consistent with the increase in alkyne π⊥ donation for 10 indicated by δ. The compound Me3SiNHC6H3Pri2-2,6 and [{WCl4(PhC2Ph)}2] gave [{WCl2(NC6H3Pri2-2,6)(PhC2Ph)(NH2C6H3Pri2-2,6)}x] 11 (δ 166.51) which with dmbipy gave cis-dichloro [WCl2(NC6H3Pri2-2,6)(PhC2Ph)(dmbipy)] 12 (δ 167.50). Other complexes prepared were [WCl2(NC6H3Me2-2,6)(PhC2Ph)(dmbipy)] 13 (δ 167.26), [WCl2(NC6H3Pri2-2,6)(PhC2Ph)(py)2] 14 (δ 158.78) and [WCl2(NC6H3Pri2-2,6)(PhC2Ph)(PMe3)2] 15 (δ 154.40). The compound Me3SiNHC6H3Pri2 –2,6 and [NEt4][WCl5(PhC2Ph)] gave [NEt4][WCl4(NHC6H3Pri2-2,6)(PhC2Ph)] 16 where δ (167.40) indicates an amido ligand allows conversion of the alkyne into a 2-electron donor.

Synthesis, structure and reactivity of [ReH 2(NR) (Cyttp)] + (Cyttp = PhP(CH 2CH 2CH 2PCy 2) 2) complexes. Organoimido analogues of the oxo complex that transfers the elements of water to substrates

The cationic organoimido-hydrido complexes [ReH 2(NR)(Cyttp)] + where R=NC 6H 4Me- p ( 2), Ph ( 3), Cy ( 4) and Cyttp = Php(CH 2CH 2CH 2PCy 2) 2 were synthesized by reaction of [ReH 2(O) (Cyttp) ]O 3SCF 3 ( 1(Tf)) with the appropriate primary amine. Use of molecular sieves promotes the formation of these rhenium products. 2–4 were shown by 1H NMR spectroscopy to contain two inequivalent, cis hydride ligands. An X-ray diffraction study of 2(PF 6) revealed the presence of distorted mer-Cyttp and the organoimido ligand cis to all three phosphorus atoms. The hydrido ligands were not located. Unlike its oxo-hydrido analogue, 1(SbF 6), 2(Tf) failed to react with CO or SO 2 under comparable, or even more forcing, conditions. However, with anhydrous HCl it afforded ReCl 3(Cyttp), and with NaBH 4, ReH 5(Cyttp).

A d0 to d2 transformation of tungsten, promoted by formation of an organoimido ligand and involving disruption of the π-perpendicular bonding component of co-ordinated diphenylacetylene

Synthetic, spectroscopic and structural investigations as well as theoretical calculations show that reaction of the d 0, four-electron donor alkyne complex [{WCl 4(PhC 2Ph)} 2] with the silylamines Me 3SiNHR (R = CMe 3, CHMe 2, CH 2Me, 2,6-CHMe 2Ph) leads to d 2, two-electron donor alkyne complexes containing organoimido ligand.

Organoimido ligands with remote functionality: a p-pyridylimido complex of vanadium(V) and its use as a metalloligand

The exposed nitrogen atom of the p-pyridylimido ligand in the vanadium(V) species [(N3N)VN-C5H4N]1{N3N =[(Me3SiNCH2CH2)3N]3–} provides a reactive site capable of complexing a second metal fragment, enabling the construction of new types of heterobimetallic complexes linked by a compact conjugated bridge.

Evaluation of the 2,6-diisopropylphenylimido ligand as a steric force in d1 and d2 monomeric octahedral complexes of tungsten

Reduction of [{WCl4(NC6H3Pri2-2,6)}2] with 2 equivalents of Na–Hg amalgam in the presence of phosphines gave the d1 complexes [WCl3(NC6H3Pri2-2,6)L2](L = PMe3, PMe2Ph or PMePh2). The crystal structure of [WCl3(NC6H3Pri2-2,6)(PMe3)2]1 shows the 2,6-diisopropylphenylimido ligand exerts a greater trans influence than a phenylimido ligand but only slightly more steric pressure. Solutions of complex 1 react with air to give [WCl3(NC6H3Pri2-2,6)(PMe3)(OPMe3)]2 for which the crystal structure shows the OPMe3 ligand lying trans to the imido ligand. Reduction of [{WCl4(NC6H3Pri2-2,6)}2] with 4 equivalents of Na–Hg amalgam in the presence of phosphines gave the d2 complexes [WCl2(NC6H3Pri2-2,6) L3](L = PMe3 or PMe2Ph). Complex [WCl2(NC6H3Pri2-2,6)(PMe3)3]3 reacts with alkynes L′ to give the complexes [WCl2(NC6H3Pri2-2,6) L′(PMe3)2](L′= PhC2Ph, MeC2Me or PhC2H) for which 1H and 13C-{1H} NMR spectral data were obtained. The crystal structure of [WCl2(NC6H3Pri2-2,6)(PhC2H)(PMe3)2]6 shows cis-chloro ligands, trans-phosphines and mutually cis-imido and alkyne ligands. The C(6) isopropyl group rotates to minimise the isopropyl group and PhC2H interaction. The complex [WCl2(NC6H3Pri2-2,6)(PhC2Ph)(PMe2Ph)2] can be prepared but not [WCl2(NC6H3Pri2-2,6)(PhC2Ph)(PMePh2)2]. Reduction of [WCl3(NC6H3Pri2-2,6)(PMe3)2](L′= CH2CH2 or CH2CHMe). A more bulky organoimido ligand or a large phosphine is needed to exert steric pressure in all the complexes prepared.

Functionalisation of [Mo6O19]2–with aromatic amines: synthesis and structure of a hexamolybdate building block with linear difunctionality

In reactions between the hexamolybdate [Mo6O19]2– and 1,4-diaminobenzene, terminal oxides are replaced by 4-aminophenylimido ligands and the first structurally characterised polyoxometallate to contain functionalised organoimido ligands, (Bun4)2[Mo6O17(NC6H4NH2)2]5, is also the first example of a trans-bis(imido) derivative; further condensation also occurs to yield species in which hexamolybdate units are linked by 1,4-phenylenediimido bridges.

Ensheathing a Polyoxometalate: Convenient Systematic Introduction of Organoimido Ligands at Terminal Oxo Sites in [Mo6O19]2-

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTEnsheathing a Polyoxometalate: Convenient Systematic Introduction of Organoimido Ligands at Terminal Oxo Sites in [Mo6O19]2-Joseph B. Strong, Robert Ostrander, Arnold L. Rheingold, and Eric A. MaattaCite this: J. Am. Chem. Soc. 1994, 116, 8, 3601–3602Publication Date (Print):April 1, 1994Publication History Published online1 May 2002Published inissue 1 April 1994https://doi.org/10.1021/ja00087a057RIGHTS & PERMISSIONSArticle Views426Altmetric-Citations79LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InReddit PDF (257 KB) Get e-AlertsSupporting Info (4)»Supporting Information Supporting Information Get e-Alerts

Diphenylacetylene complexes of tungsten containing π-acceptor ligands

Reaction of PhC2Ph with [WCl2(PhC2Ph)(PMe3)3] gave [WCl2(PhC2Ph)2(PMe3)2]1 for which IR and NMR spectral data indicated cis-chloro ligands. trans phosphines and mutually-cis diphenylacetylene ligands. This geometry was confirmed by X-ray crystallography. The average W–C bond lengths are 2.071 (3)A. The 13C NMR spectrum showed the acetylenic carbon resonance at δ 185.45. The alkynes HC2H and PhC2H reacted with [WCl2(PhC2Ph)(PMe3)3] giving [WCl2(PhC2Ph)(HC2H)(PMe3)2]2 and [WCl2(PhC2Ph)(PhC2H)(PMe3)2]3. The phenylacetylene ligand gave rise to asymmetry in complex 3 leading to an AB system 31P-{1H} NMR spectrum. Different values of 1J(PW) indicated small differences in the W–P bonding. Alkyl-substituted acetylenes did not react cleanly with [WCl2(PhC2Ph)(PMe3)3]. The complexes [WCl2(PhC2Ph)(PrnC2Me)(PMe3)2]4 and [WCl2(PhC2Ph)(MeC2Me)(PMe3)2]5 were prepared by sodium–mercury amalgam reduction of [WCl3(PhC2Ph)(PMe3)2] with hex-2-yne or but-2-yne present but were not particularly stable in solution. Sodium-mercury amalgam reduction of [WCl3(PhC2Ph)(PMe3)2] under ethylene or propene gave [WCl2(PhC2Ph)(CH2CH2)(PMe3)2]6 or [WCl2(PhC2Ph)(MeCHCH2)(PMe3)2]9. Complex 9 was unstable in solution and was characterised by NMR spectroscopy. The 13C NMR acetylenic carbon resonances in complexes 6 and 9 are at δ 218.11 and 218.82. Reduction of [WCl3(PhC2Ph)(PMe3)2] under cis- or trans-but-2-ene or 2-methylpropene afforded [WCl2(PhC2Ph)(PMe3)3] and [WCl2(PhC2Ph)(PMe3)2]x10 as characterised by NMR spectroscopy. Reduction of [WCl3(PhC2Ph)L2](L = PMe3or PMePh2) under CO gave [WCl2(PhC2Ph)(CO)(PMe3)2]11 and [WCl2(PhC2Ph)(CO)(PMePh2)2]12 for which X-ray crystal structure determinations showed cis-chloro ligands, trans phosphines and mutually-cis PhC2Ph and CO ligands. The W–C and C–C bond lengths for complex 11 are 2.009(5), 2.024(5) and 1.341 (6)A, respectively. Overall the reactions showed that the diphenylacetylene ligand in these complexes acts like an organoimido or oxo ligand.

A polyoxometalate incorporating an organoimido ligand: preparation and structure of [Mo5O18(MoNC6H4CH3)]2-

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTA polyoxometalate incorporating an organoimido ligand: preparation and structure of [Mo5O18(MoNC6H4CH3)]2-Yuhua Du, Arnold L. Rheingold, and Eric A. MaattaCite this: J. Am. Chem. Soc. 1992, 114, 1, 345–346Publication Date (Print):January 1, 1992Publication History Published online1 May 2002Published inissue 1 January 1992https://doi.org/10.1021/ja00027a046RIGHTS & PERMISSIONSArticle Views612Altmetric-Citations141LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InReddit PDF (286 KB) Get e-AlertsSupporting Info (1)»Supporting Information Supporting Information Get e-Alerts