Synthesis, structure and electrochemical studies of the first mixed-metal clusters with the P–N–P assembling ligands (Ph2P)2NH (dppa), (Ph2P)2N(CH3) (dppam) and (Ph2P)2N(CH2)3Si(OEt)3 (dppaSi)

Bachert, Isolde; Braunstein, Pierre; McCart, Mark K.; Biani, Fabrizia Fabrizi de; Laschi, Franco; Zanello, Piero; Kickelbick, Guido; Schubert, Ulrich

doi:10.1016/s0022-328x(98)00636-6

Cited by 46 publications

(24 citation statements)

References 13 publications

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“…Due to smaller ionic radii, no interaction between lithium and phosphorus atoms was observed. Li-N bond length 2.08 (2) 2 ] complex, and also similar to literature reports. [24] The Li-O distances of 1.93(2) and 1.91(2) Å were within the range of reported values.…”

Section: Lithium Complexsupporting

confidence: 90%

“…The molecular structure of complex 5 is given in Figure 2. [47] These Ba-N distances were also slightly elongated compared to the previously reported barium complexes [Ba(THF) 2 The Ba-P [3.6875(7) and 3.7115(7) Å] distances were considerably elongated in barium bis(borane-diphenylphosohino)amide complex (5) and were greater than the sum of the covalent radii of barium and phos-www.zaac.wiley-vch.de ARTICLE phorus (3.34 Å), thereby indicating that barium and phosphorus had no interaction between themselves. Thus, in complex 5, the central atom barium adopted a distorted-snub-disphenoidal arrangement having 12 faces due to the ligation from two ligand (1) moieties and two THF molecules (see Figure 3).…”

Section: Alkaline Earth Metal Complexes 3-5mentioning

confidence: 65%

“…We were therefore interested in modeling the calcium (3) and strontium (4) metal complexes, whose crystals were weakly diffracted in the Xray. In addition, by optimizing their structure computationally, we wanted more insight into the structure and bonding of the barium complex 5 along with analogous complexes [{η 2 (8), and the diselenoimidodiphosphinato ligand (1Ј) that was reported by us earlier. [38] For a better comparison, we have studied six metal complexes through computational methods in this paper.…”

Section: Computational Analysismentioning

confidence: 99%

“…[2] The greater acidity of the NH proton as compared to the CH 2 protons may facilitate subsequent functionalization reactions that would require very drastic conditions in the case of dppm. Besides, some theoretical studies single-crystal X-ray diffraction analysis.…”

Section: Introductionmentioning

confidence: 99%

“…These μ-bis(dialkylphosphanyl)-alkane]bis[pentacarbonyl-metal(0)] complexes (CO) 5 MR 2 P(NH)-PR 2 M(CO) 5 (M = Cr, Mo, W) were synthesized from the reaction of M(CO) 5 (CH 3 CN) with the dppa ligand. [2,[5][6][7] The chalcogen (sulfur and selenium) functionalized dppa derivatives were also well defined to stabilize metal complexes by the formation of chalcogen metal bonds. [8,9,10] These unique ligands are potentially capable of coordinating through the hard nitrogen and phosphorus donor atoms along with the soft chalcogen donor atom to provide the highest coordination sphere of the metal ion required for its stabilization.…”

Section: Introductionmentioning

confidence: 99%

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Alkali Metal and Alkaline Earth Metal Complexes with the Bis(borane‐diphenylphosphanyl)amido Ligand – Synthesis, Structures, and Catalysis for Ring‐Opening Polymerization of ϵ‐Caprolactone

Bhattacharjee

Das

Reddy

et al. 2015

Zeitschrift anorg allge chemie

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Abstract. The syntheses of lithium and alkaline earth metal complexes with the bis(borane-diphenylphosphanyl)amido ligand (1-H) of molecular formulas [{κ 2 -N(PPh 2 (BH 3 )) 2 }Li(THF) 2 ] (2) and (3), Sr (4), Ba (5)] are reported. The lithium complex 2 was obtained by treatment of bis(borane-diphenylphosphanyl)amine (1-H) with lithium bis(trimethylsilyl)-amide in a 1:1 molar ratio via the silylamine elimination method. The corresponding homoleptic alkaline earth metal complexes 3-5 were prepared by two synthetic routes -first, the treatment of metal bis(trimethylsilyl)amide and protio ligand 1-H via the elimination of silylamine, and second, through salt metathesis reaction involving respective metal diiodides and lithium salt 2. The molecular structures of lithium complex 2 and barium complex 5 were established by

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Section: Lithium Complexsupporting

confidence: 90%

Section: Alkaline Earth Metal Complexes 3-5mentioning

confidence: 65%

Section: Computational Analysismentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Alkali Metal and Alkaline Earth Metal Complexes with the Bis(borane‐diphenylphosphanyl)amido Ligand – Synthesis, Structures, and Catalysis for Ring‐Opening Polymerization of ϵ‐Caprolactone

Bhattacharjee

Das

Reddy

et al. 2015

Zeitschrift anorg allge chemie

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Strategies for the Anchoring of Metal Complexes, Clusters, and Colloids Inside Nanoporous Alumina Membranes

et al. 2000

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Two complementary strategies are presented for the anchoring of molecular palladium complexes, of cobalt or platinum clusters or of gold colloids inside the nanopores of alumina membranes. The first consists in the one step condensation of an alkoxysilyl functional group carried by the metal complex with the hydroxy groups covering the surface of the membrane pores. Thus, using the short-bite alkoxysilyl-functionalized diphosphane ligands (Ph2P)2N(CH2)3Si(OMe)3 (1) and (Ph2P)2N(CH2)4SiMe2(OMe)] (2) derived from (Ph2P)2NH (dppa) (dppa bis(diphenylphosphanyl)amine), the palladium complexes [Pd(dmba)(kappa2-P,P-(Ph2P)2N(CH2)3Si(OMe)3)] Cl (3) and [Pd(dmba)[kappa2-P,P-(Ph2P)2N(CH2)4SiMe2(OMe)]]Cl (4) (dmba-H = dimethylbenzylamine). respectively, were tethered to the pore walls. After controlled thermal treatment. confined and highly dispersed palladium nanoparticles were formed and characterized by transmission electron microscopy (TEM). This method could not be applied to the cobalt cluster [Co4(CO)8(mu-dppa)[mu-P,P-(Ph2P)2N(CH2)4SiMe2(OMe)]] (7) owing to its too limited solubility. However, its anchoring was achieved by using the second method which consisted of first derivatizing the pore walls with 1 or 2. The covalent attachment of the diphosphane ligands provides a molecular anchor that allows subsequent reaction with the cluster [Co4(CO)10(mu-dppa)] 6 to generate anchored 7 and this step was monitored by UV/Vis spectroscopy. In addition, the presence of carbonyl ligands in the cluster provides for the first time a very sensitive spectroscopic probe in the IR region which confirms both cluster incorporation and the retaining of its molecular nature inside the membrane. The presence of the bridging dppa ligand in 6 provides additional stabilization and accounts for the selectivity of the procedure. Using this method, platinum clusters (diameter ca. 2 nm) and gold colloids (diameter ca. 13 nm) were immobilized after passing their solution through the functionalized membrane pores. The resulting membranes were characterized by TEM which demonstrated the efficiency of the complexation and showed the high dispersion of the metal loading. The successful application of these methods has demonstrated that nanoporous alumina membranes are not only unique supports to incorporate metal complexes, clusters, or colloids but can also be regarded as functional matrices or microreactors, thus opening new fields for applications.

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On the Reactivity of the Iminodiphosphane C₆H₄(o‐CN)N=PPh₂−PPh₂: Fragmentation Versus Isomerisation

2004

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The reactivity of the iminodiphosphane C6H4(o‐CN)N=PPh2−PPh2, which contains an N=P−P unit, has been investigated. Reaction with small molecules, [viz. H2O/O2, H2O2, CH3OH, C6H4(o‐CN)NH2] and elemental sulfur result in cleavage of the P−P bond to give aminophosphane‐derivatised compounds. The products from these reactions have been characterized spectroscopically, including two by single‐crystal X‐ray diffraction. The reactivity of the iminodiphosphane towards the transition metal complexes [M(cod)Cl2] (M = Pd or Pt) has also been investigated. In the reactions, the iminodiphosphane rearranges to form the more common diphosphonylamine (P−N−P) unit which chelates to the metal centres. Three different compounds were isolated from these reactions and they have all been fully characterised by spectroscopy and single‐crystal X‐ray diffraction. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)

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Synthesis, structure and electrochemical studies of the first mixed-metal clusters with the P–N–P assembling ligands (Ph2P)2NH (dppa), (Ph2P)2N(CH3) (dppam) and (Ph2P)2N(CH2)3Si(OEt)3 (dppaSi)

Cited by 46 publications

References 13 publications

Alkali Metal and Alkaline Earth Metal Complexes with the Bis(borane‐diphenylphosphanyl)amido Ligand – Synthesis, Structures, and Catalysis for Ring‐Opening Polymerization of ϵ‐Caprolactone

Alkali Metal and Alkaline Earth Metal Complexes with the Bis(borane‐diphenylphosphanyl)amido Ligand – Synthesis, Structures, and Catalysis for Ring‐Opening Polymerization of ϵ‐Caprolactone

Strategies for the Anchoring of Metal Complexes, Clusters, and Colloids Inside Nanoporous Alumina Membranes

On the Reactivity of the Iminodiphosphane C₆H₄(o‐CN)N=PPh₂−PPh₂: Fragmentation Versus Isomerisation

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Synthesis, structure and electrochemical studies of the first mixed-metal clusters with the P–N–P assembling ligands (Ph2P)2NH (dppa), (Ph2P)2N(CH3) (dppam) and (Ph2P)2N(CH2)3Si(OEt)3 (dppaSi)

Cited by 46 publications

References 13 publications

Alkali Metal and Alkaline Earth Metal Complexes with the Bis(borane‐diphenylphosphanyl)amido Ligand – Synthesis, Structures, and Catalysis for Ring‐Opening Polymerization of ϵ‐Caprolactone

Alkali Metal and Alkaline Earth Metal Complexes with the Bis(borane‐diphenylphosphanyl)amido Ligand – Synthesis, Structures, and Catalysis for Ring‐Opening Polymerization of ϵ‐Caprolactone

Strategies for the Anchoring of Metal Complexes, Clusters, and Colloids Inside Nanoporous Alumina Membranes

On the Reactivity of the Iminodiphosphane C6H4(o‐CN)N=PPh2−PPh2: Fragmentation Versus Isomerisation

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On the Reactivity of the Iminodiphosphane C₆H₄(o‐CN)N=PPh₂−PPh₂: Fragmentation Versus Isomerisation