Skeletal isomerism in mixed transition-metal/main-group closo clusters

Guechtouli, Nabila; Lucas, Guillaume; Boucekkine, Abdou; Halet, Jean‐François; Kahlal, Samia; Lokbani-Azzouz, Nabila Suad; Meghezzi, Hacène; Saillard, Jean‐Yves

doi:10.1016/j.crci.2005.02.035

Cited by 5 publications

(3 citation statements)

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“…It turned out, however, that the so called 2nd hexol is of composition [Co 6 (OH) 8 (O) 2 (NH 3 ) 14 ] 6+ , thus being a chemically different species.65 For [Au 9 {P(C 6 H 4 OMep) 3 } 8 ](NO 3 ) 3 Briant et al66 have reported two different crystalline modifications as the first example of skeletal isomerism in metal cluster chemistry. More recent examples for skeletal isomerism in mixed transition-metal/main-group closo clusters have summarised by Guechtouli et al67 For multinuclear complexes Haupt has reported on the crystallographic characterisation of several different pairs of constitutional isomers of trinuclear complexes possessing a different structural skeleton 68.…”

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Phosphite copper(i) trifluoroacetates [((RO)3P)mCuO2CCF3] (m = 1, 2, 3): synthesis, solid state structures and their potential use as CVD precursors

Mothes¹,

Rüffer²,

Shen³

et al. 2010

Dalton Trans.

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Metal-organics [((RO)(3)P)(m)CuO(2)CCF(3)] (R = CH(3): 11a, m = 1; 11b, m = 2; 11c, m = 3. R = CH(2)CH(3): 12a, m = 1; 12b, m = 2; 12c, m = 3. R = CH(2)CF(3): 13a, m = 1; 13b, m = 2; 13c, m = 3) are either accessible by the reaction of [((RO)(3)P)(m)CuCl] (R = CH(3): 5a, m = 1; 5b, m = 2; 5c, m = 3. R = CH(2)CH(3): 6a, m = 1; 6b, m = 2; 6c, m = 3) with [KO(2)CCF(3)] (7), or treatment of [Cu(2)O] (8) with HO(2)CCF(3) (9) and P(OR)(3) (2, R = CH(3); 3, R = CH(2)CH(3); 4, R = CH(2)CF(3)). (31)P{(1)H} NMR spectra [((CH(3)O)(3)P)(m)CuO(2)CCF(3)] (m = 1, 1.5, 2, 2.5, 3, 3.5, and 4) have been studied at 25 and -80 °C showing phosphite ligand exchange in solution. The molecular structures of 11a and 13a-13c in the solid state are reported. Complexes 11a and 13a are tetramers featuring μ-η(2)(1κO:2κO')- and μ(3)-η(2)(1κO:2κO':3κO')-(11a) or μ(3)-η(2)(1κO:2κO':3κO')-bonded O(2)CCF(3) ligands (13a) with the Cu(I) ions being part of CuPO(2) and CuPO(3) units (11a), while in 13a solely a CuPO(3) moiety is present. Skeletal isomerism of 11a vs. 13a is discussed. Compound 13b is dimeric ({CuP(2)O(2)}(2)) with pseudo-tetrahedral Cu environments and μ-η(2)(1κO:2κO')O(2)CCF(3) functionalities. In monomeric 13c the O(2)CCF(3) ligand is η(1)(κO)-bonded to a tetra-coordinated Cu(i) ion. The thermal solid state properties of 11, 12 and 13 were studied by Thermo Gravimetry (TG). These complexes decompose by phosphite elimination, decarboxylation and dealkylation. Hot-wall Chemical Vapour Deposition (CVD) experiments were carried out at 380 °C using 11c as precursor for the deposition of copper onto pieces of TiN-coated oxidized silicon substrates. Copper layers of high purity were obtained with grain sizes between 200-1200 nm.

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Phosphite copper(i) trifluoroacetates [((RO)3P)mCuO2CCF3] (m = 1, 2, 3): synthesis, solid state structures and their potential use as CVD precursors

Mothes¹,

Rüffer²,

Shen³

et al. 2010

Dalton Trans.

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“…We have shown previously that such an architecture is, in the case of E = N, particularly favored for an electron count of 6 SEPs, i.e. four less electrons than the clusters investigated in this work [15]. The case of E = NH is somewhat different.…”

Section: Resultsmentioning

confidence: 55%

“…Other limitations are related to skeletal isomerism as for example mixed transition/main group clusters. Indeed, there are often several ways to distribute atoms of different nature on the different vertices of the same polyhedron, leading to the possibility of different structures for the same electron count, the PSEP being unable to predict which one is the most stable [14,15]. Limitations can also occur when cluster bonding lies at the boundary between localization and delocalization.…”

Section: Introductionmentioning

confidence: 99%

Structural Diversity Within the Series of 68-Electron M4L n E2 (L = 2-Electron Ligand; M = Fe, Ru, Os, Co; E = CH, N, P, NR, PR, S) Organometallic Clusters: A Theoretical Investigation

et al. 2012

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Four different skeletal structural arrangements with very different connectivities are known for 6-vertex/68-electron of M 4 E 2 core (M = transition metal; E = main-group atom or ligand). DFT calculations on a large number of title model compounds allow to rationalize the preferences between these structural shapes with respect to the nature of the metal and main-group elements constituting the cluster cage. In particular, the electronegativity of M and the ''size'' (first-row vs. second-row element) of E play an important role in the stability preference of a particular isomer. For several compounds, although only one type of structure is known, other low-energy isomeric forms are also likely to exist. Moreover, two structural types, so far unreported, are predicted to be stable enough for being synthesized.Dedicated to our friend Richard D. Adams on the occasion of his 65th birthday.Electronic supplementary material The online version of this article (

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Computational Methods: Transition Metal Clusters

Gautier¹,

Halet²,

Saillard³

2005

Encyclopedia of Inorganic Chemistry

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Cluster chemistry is dominated by structural aspects. Indeed, structure and bonding are strongly related to stability and properties, and cluster structures are particularly diverse and often complex. Thus, electron‐counting rules, which relate structure to electron count, have been the key to the development of cluster chemistry as a distinct area of chemistry. These rules have been set up progressively along time with the help of quantum chemistry. This article deals with the recent progress on transition metal and mixed main group/transition metal cluster chemistry arising from the contribution of modern computational theory to the rationalization of structures. This article focuses on “viable” species, i.e., molecules that are isolable under reasonable conditions and deals with the exploration of the limitations of the classical electron‐counting rules as well as the establishment of new rules for new structural types with the help of quantum chemical calculations.

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Skeletal isomerism in mixed transition-metal/main-group closo clusters

Cited by 5 publications

References 64 publications

Phosphite copper(i) trifluoroacetates [((RO)3P)mCuO2CCF3] (m = 1, 2, 3): synthesis, solid state structures and their potential use as CVD precursors

Phosphite copper(i) trifluoroacetates [((RO)3P)mCuO2CCF3] (m = 1, 2, 3): synthesis, solid state structures and their potential use as CVD precursors

Structural Diversity Within the Series of 68-Electron M4L n E2 (L = 2-Electron Ligand; M = Fe, Ru, Os, Co; E = CH, N, P, NR, PR, S) Organometallic Clusters: A Theoretical Investigation

Computational Methods: Transition Metal Clusters

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