Showing papers by "M. Teresa Moreno published in 2004"
TL;DR: In this paper, the photoluminescent properties of bimetallic compounds with cyclen and tetranuclear derivatives have been investigated, showing that they are stabilized by a short Pt→Cd donor acceptor bond and that the Cd center is also coordinated to the Cα of one of the two alkynyl groups.
48 citations
TL;DR: The solid-state structures of phenyl derivatives have been determined by X-ray crystallography and the terminal alkynyl ligands in these cyanide-bridged molecular squares 3 and 4 have been used in the assembly of higher multimetallic complexes.
Abstract: Novel mixed bis(alkynyl)bis(cyano)platinate(II) species [cis-Pt(Ctbond;CR)(2)(CN)(2)](2-) (1 a: R = tBu, 1 b: R = Ph) have been prepared and their potential as building blocks in the generation of self-organized systems with a variable molecular architecture has been studied. The reaction of 1 with the ditopic acceptor species [[cis-Pt(C(6)F(5))(2)S](2)(dppa)] (dppa=diphenylphosphinoacetylene) gave the dianionic cyanide/dppa bridged molecular platinotriangles (NBu(4))(2)[(C(6)F(5))(2)Pt(micro-dppa)[(micro-CN)(2)Pt(Ctbond;CR)(2)]Pt(C(6)F(5))(2)] (2). X-ray analysis of 2 a confirmed that the "Pt(2)(C(6)F(5))(4)(micro-dppa)" binuclear moiety is connected to the dianionic "Pt(Ctbond;CR)(2)(CN)(2)" unit by two bridging cyanide ligands. Moreover, treatment of 1 with the solvent cationic species [M(cod)(acetone)(2)](+) afforded heterometallic molecular squares Pt(2)M(2) (M=Rh, Ir) containing cyanide bridges and terminal alkynyl ligands, (NBu(4))(2)[cyclo[[cis-Pt(Ctbond;CR)(2)(micro-CN)(2)][M(cod)]](2)] (3: M=Rh, 4: M = Ir). The solid-state structures of phenyl derivatives have been determined by X-ray crystallography. The terminal alkynyl ligands in these cyanide-bridged molecular squares 3 and 4 have been used in the assembly of higher multimetallic complexes. Thus, very unusual bis(double-alkynide)-cyanide-bridged hexametallic compounds (NBu(4))(2)[[(C(6)F(5))(2)Pt(micro-Ctbond;CPh)(2)(micro-CN)(2)](2)[M(cod)](2)] (5 b: M=Rh, 6 b: M = Ir) were easily formed by simple reactions of 3 b and 4 b with two equivalents of [cis-Pt(C(6)F(5))(2)(thf)(2)]. An X-ray diffraction study on complex 5 b indicated that the derivative was formed by a simultaneous migration of one sigma-alkynyl group from each "Pt(Ctbond;CPh)(2)(micro-CN)(2)" corner of the square to both "Pt(C(6)F(5))(2)" units, resulting in bent sigma,pi-double-alkynyl bridging systems. Finally, the novel supramolecular anionic assemblies (NBu(4))(4)[cyclo[[cis-Pt(Ctbond;CR)(2)(micro-CN)(2)][SnPh(3)]](4)] 7 have been obtained by self-assembly of 1 and [SnPh(3)(acetone)(2)](+).
40 citations
TL;DR: The synthesis and characterization of a series of mononuclear d(8) complexes with at least two P-coordinated alkynylphosphine ligands and their reactivity toward cis-[Pt(C(6)F(5))(2)(THF)(2)] are reported.
Abstract: The synthesis and reactivity toward cis-[Pt(C6F5)2(THF)2] of several alkynylphosphine d8 complexes, [Pt(C6F5)(PPh2C⋮CPh)3](CF3SO3), 1, [M(COD)(PPh2C⋮CPh)2](ClO4) (M = Rh, 2, and Ir, 3), and [Pt(o-C6H4E2)(PPh2C⋮CPh)2] (E = O, 6, and S, 7), are reported. Whereas 1 gives rise to the diinserted product 8, which evolves in solution to the bis(diphenylphosphine)naphthalene-based mononuclear complex 9, analogous reactions with 2 or 3 give mixtures of products. The reactions with 6 or 7 afford binuclear heterobridged (μ-κE-o-C6H4E2)/(μ-κP:η2-PPh2C⋮CPh) 11 and 12 or trinuclear (μ3-κ2EE‘-o-C6H4E2)/(μ-κP:η2-PPh2C⋮CPh)2 13 and 14 complexes.
28 citations
TL;DR: A series of mononuclear platinum complexes containing diynyldiphenylphosphine ligands is synthesized and the X-ray crystal structures of 4a and 4b have been determined to compare the eta2-bonding capability of the inner and outer alkyne units.
Abstract: A series of mononuclear platinum complexes containing diynyldiphenylphosphine ligands [cis-Pt(C6F5)2(PPh2CCC6H4CCR)L]n
(n
= 0, L = tht, R = Ph 2a, But2b; L = PPh2CCC6H4CCR, 4a, 4b; n
=
−1, L = CN−, 3a, 3b) has been synthesized and the X-ray crystal structures of 4a and 4b have been determined. In order to compare the η2-bonding capability of the inner and outer alkyne units, the reactivity of 2–4 towards [cis-Pt(C6F5)2(thf)2] or [Pt(η2-C2H4)(PPh3)2] has been examined. Complexes 2 coordinate the fragment “cis-Pt(C6F5)2” using the inner alkynyl fragment and the sulfur of the tht ligand giving rise the binuclear derivatives [(C6F5)2Pt(µ-tht)(µ-1κP:2η2-Cα,Cβ-PPh2CCC6H4CCR)Pt(C6F5)2]
(R = Ph 5a, But5b). The phenyldiynylphosphine complexes 2a, 3a and 4a react with [Pt(η2-C2H4)(PPh3)2] to give the mixed-valence Pt(II)–Pt(0) complexes [{(C6F5)2LPt(µ-1κP:2η2-C5,C6-PPh2CCC6H4CCPh)}Pt(PPh3)2]n
(L = tht 6a, CN 8a and PPh2CCC6H4CCPh 9a) in which the Pt(0) fragment is η2-complexed by the outer fragment. Complex 6a isomerizes in solution to a final complex [{(C6F5)2(tht)Pt(µ-1κP:2η2-Cα,Cβ-PPh2CCC6H4CCPh)}Pt(PPh3)2]
7a having the Pt(0) fragment coordinated to the inner alkyne function. In contrast, the tert-butyldiynylphosphine complexes 2b and 3b coordinate the Pt(0) unit through the phosphorus substituted inner acetylenic entity yielding 7b and 8b. By using 4a and 2 equiv. of [Pt(η2-C2H4)(PPh3)2] as precursors, the synthesis of the trinuclear complex [cis-{(C6F5)2Pt(µ-1κP:2η2-C5,C6-PPh2CCC6H4CCPh)2}(Pt(PPh3)2)2]
10a, bearing two Pt(0)(PPh3)2
η2-coordinated to the outer alkyne functions is achieved. The structure of 7a has been confirmed by single-crystal X-ray diffraction.
15 citations