Pt[In-C(SiMe3)3]4 - eine zu Pt(CO)4 analoge Verbindung mit einem durch vier InR-Liganden ideal tetraedrisch koordinierten Platinatom

Uhl, Werner; Melle, Sandra

doi:10.1002/1521-3749(200010)626:10<2043::aid-zaac2043>3.0.co;2-4

Cited by 41 publications

(25 citation statements)

References 7 publications

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“…The first example has been reported by Uhl et al who synthesized the compounds Ni(ER) 4 with E ϭ In [5] and Ga [6] where R are bulky silyl groups. The analogous platinum complex with an indium-diyl ligand Pt(InR) 4 has in the meantime also been prepared [7]. There seems to be no significant difference between the stabilities of the nickel and platinum complexes M(InR) 4 [5Ϫ7].…”

Section: Introductionmentioning

confidence: 99%

Why are the Homoleptic Diyl Complexes M(InR)4 with M = Ni and Pt Stable Compounds while only Ni(CO)4 but not Pt(CO)4 can become Isolated? A Theoretical Study of M(EMe)44 and M(CO)4 (M = Ni, Pd, Pt; E = B, Al, Ga, In, Tl)

Doerr

Frenking

2002

Z. anorg. allg. Chem.

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The equilibrium geometries and first bond dissociation energies of the homoleptic complexes M(EMe) 4 and M(CO) 4 with M ϭ Ni, Pd, Pt and E ϭ B, Al, Ga, In, Tl have been calculated at the gradient corrected DFT level using the BP86 functionals. The electronic structure of the metal-ligand bonds has been examined with the topologial analysis of the electron density distribution. The nature of the bonding is revealed by partitioning the metalligand interaction energies into contributions by electrostatic attraction, covalent bonding and Pauli repulsion. The calculated data show that the M-CO and M-EMe bonding is very similar. However, the M-EMe bonds of the lighter elements E are much stronger than the M-CO bonds. The bond energies of the latter are as low or even lower than the M-TlMe bonds. The main reason why Pd(CO) 4 and Pt(CO) 4 are unstable at room temperature in a condensed phase can be traced back to the already rather weak bond energy of the Ni-CO bond. The Pd-L bond energies of the complexes with Theoretische Studien anorganischer Verbindungen. 17 Warum sind die homoleptischen Diyl-Komplexe M(InR) 4 mit M ‫؍‬ Pt und Ni stabile Verbindungen obwohl nur Ni(CO) 4 nicht aber Pt(CO) 4 isoliert werden kann? Eine theoretische Untersuchung von M(EMe) 4 und M(CO) 4 (M ‫؍‬ Ni, Pd, Pt; E ‫؍‬ B, Al, Ga, In, Tl) Inhaltsübersicht. Die Geometrien und erste Dissoziationsenergien der homoleptischen Komplexe M(EMe) 4 und M(CO) 4 mit M ϭ Ni, Pd, Pt und E ϭ B, Al, Ga, In, Tl wurden mit gradientenkorrigierten Dichtefunktionalen unter Verwendung von BP86 berechnet. Die elektronische Struktur der Metall-Ligand-Bindungen ist mit der topologischen Analyse der Elektronendichteverteilung untersucht worden. Die Natur der chemischen Bindung wurde durch eine Energieanalyse aufgeklärt, mit deren Hilfe die Beiträge der elektrostatischen Anziehung, der kovalenten Bindung und der Pauli-Abstoßung zu den Metall-Ligand-Wechselwirkungen ermittelt wurden. Die Ergebnisse zeigen, dass die M-CO-and M-EMe-Bindungen sehr ähnlich sind. Die M-EMe-Bindungen der leichteren Elemente E sind aber wesentlich stärker als die M-CO-Bindungen. Die Metall-Carbonyl-Bindungen haben eine ähnlich geringe Bindungsenergie wie die M-TlR-Bindungen. Die Erklärung, warum Pd(CO) 4 und Pt(CO) 4 in kondensierter Phase bei Raumtemperatur instabil sind, findet ihren Ursprung in der bereits geringen /0 843 L ϭ CO and L ϭ EMe are always 10 Ϫ 20 kcal/mol lower than the Ni-L bond energies. The calculated bond energy of Ni(CO) 4 is only D o ϭ 27 kcal/mol. Thus, the bond energy of Pd(CO) 4 is only D o ϭ 12 kcal/mol. The first bond dissociation energy of Pt(CO) 4 is low because the relaxation energy of the Pt(CO) 3 fragment is rather high. The low bond energies of the M-CO bonds are mainly caused by the relatively weak electrostatic attraction and by the comparatively large Pauli repulsion. The σ and π contributions to the covalent M-CO interactions have about the same strength. The π bonding in the M-EMe bonds is less than in the M-CO bonds but it remains an important part of the bon...

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Section: Introductionmentioning

confidence: 99%

Why are the Homoleptic Diyl Complexes M(InR)4 with M = Ni and Pt Stable Compounds while only Ni(CO)4 but not Pt(CO)4 can become Isolated? A Theoretical Study of M(EMe)44 and M(CO)4 (M = Ni, Pd, Pt; E = B, Al, Ga, In, Tl)

Doerr

Frenking

2002

Z. anorg. allg. Chem.

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“…The monomer of the cluster (InR) is isolobal to carbon monoxide, and several transition metal carbonyl analogous compounds were obtained with bridging or terminal InR ligands. Among these the tetracarbonylnickel analogues Ni[InC(SiMe 3 ) 3 ] 4 [4] and Pt[InC-(SiMe 3 ) 3 ] 4 [5] are of particular interest, because considerable p-back bonding of electron density from the central metal atoms into the empty p orbitals of the indium atoms was verified by quantum-chemical calculations. [6] Furthermore, these monomeric InR fragments were trapped by cycloaddition reactions.…”

Section: Introductionmentioning

confidence: 99%

Alkylindium Subhalides Derived from the Tetrahedral Indium(I) Cluster Compound [In4{C(SiMe3)3}4]

Uhl

Melle

2001

Chem. Eur. J.

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Partial oxidation of the tetraalkyltetraindium(I) compound In4[C(SiMe3)3]4] 1 with halogen donors such as 1,2-dibromoethane and hexachloroethane or with mixtures of bromine and aluminum tribromide afforded novel alkylindium halides in which the indium atoms still possess unusually low oxidation states. Indium-indium single bonds between bivalent indium atoms were found in the compounds In2X2R2 (R = C(SiMe3)3, X = Cl (2) or Br (4)), which gave dimers in the solid state with all four halogen atoms in a bridging position. The tetrahedral arrangement of four indium atoms in a cluster was retained in the compound In4Br2R4 (3), in which one bromine atom occupied a mu3-bridging position above one triangular face of the In4 tetrahedron. One edge of that triangle was bridged by the second bromine atom. Mixed-valent indium atoms resulted with an average oxidation state of + 1.5.

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“…Diese monomeren Fragmente der Cluster sind isolobal zu Kohlenmonoxid, und in der Tat ließen sich zahlreiche Komplexe mit GaR-oder InR-Liganden synthetisieren, die Analoga zu Übergangsmetallcarbonylen darstellen und in denen verbrückende CO-Liganden ersetzt wurden [6]. Besonders hervorzuheben sind jedoch Verbindungen des Typs Ni(ER) 4 [7,8] oder Pt(ER) 4 [9], in denen die Übergangsmetallatome ideal tetraedrisch von vier Gaoder In-Atomen mit sehr kurzen M-E-Abständen umgeben sind. Sie entsprechen in ihrer Konstitution dem Carbonylkomplex Ni(CO) 4 , und, wie quantenchemische Untersuchungen zeigen, verfügen sie wie dieser über eine starke Rückbindung von Elektronendichte vom Zentralatom in unbesetzte Orbitale mit π-Symmetrie am Liganden.…”

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Ga₂Br₂R₂ und Ga₃I₂R₃ [R = C(SiMe₃)₃] — zwei neue elementorganische Galliumsubhalogenide mit einer bzw. zwei Ga‐Ga‐Bindungen

Uhl

El‐Hamdan

Geiseler

et al. 2004

Zeitschrift anorg allge chemie

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Professor Werner Massa zum 60. Geburtstag gewidmet Inhaltsübersicht. Die vorsichtige Oxidation des tetraedrischen Tetragalliumclusters Ga 4 [C(SiMe 3 ) 3 ] 4 (1) mit elementarem Brom in Gegenwart von AlBr 3 führt zur Bildung des entsprechenden Subhalogenids Ga 2 Br 2 R 2 [4, R ϭ C(SiMe 3 ) 3 ], das überraschenderweise selbst im Festkörper monomer vorliegt und in dem die zweiwertigen Galliumatome über eine kurze Ga-Ga-Einfachbindung [243,2(2) pm] miteinander verbunden sind. Die analoge Digalliumdiiod-Verbindung Ga 2 I 2 R 2 (3), die bereits früher in unserer Arbeitsgruppe auf ähnlichem Weg erhalten wurde, reagiert mit Lithium-tert-butanolat nicht unter Substitution, sondern unter teilweiser Disproportionierung zu dem Trigalliumdiiodid Ga 3 I 2 R 3 (6), Abstract. The oxidation of the tetrahedral tetragallium cluster Ga 4 [C(SiMe 3 ) 3 ] 4 (1) with elemental bromine in the presence of AlBr 3 yielded the corresponding gallium subhalide Ga 2 Br 2 R 2 [4, R ϭ C(SiMe 3 ) 3 ], which remains monomer even in the solid state and in which the Ga II atoms are connected by a short Ga-Ga single bond [243.2(2) pm]. The analogous diiodide Ga 2 I 2 R 2 (3), which was obtained on a similar route by our group only recently, did not react with lithium tert-butanolate by substitution as originally expected. Instead, partial disproportionation occurred with the formation of the trigallium diiodide Ga 3 I 2 R 3 (6), in which three Ga atoms are connected by two Ga-Ga single bonds (255.1 pm on av-

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Pt[In-C(SiMe3)3]4 - eine zu Pt(CO)4 analoge Verbindung mit einem durch vier InR-Liganden ideal tetraedrisch koordinierten Platinatom

Cited by 41 publications

References 7 publications

Why are the Homoleptic Diyl Complexes M(InR)4 with M = Ni and Pt Stable Compounds while only Ni(CO)4 but not Pt(CO)4 can become Isolated? A Theoretical Study of M(EMe)44 and M(CO)4 (M = Ni, Pd, Pt; E = B, Al, Ga, In, Tl)

Why are the Homoleptic Diyl Complexes M(InR)4 with M = Ni and Pt Stable Compounds while only Ni(CO)4 but not Pt(CO)4 can become Isolated? A Theoretical Study of M(EMe)44 and M(CO)4 (M = Ni, Pd, Pt; E = B, Al, Ga, In, Tl)

Alkylindium Subhalides Derived from the Tetrahedral Indium(I) Cluster Compound [In4{C(SiMe3)3}4]

Ga₂Br₂R₂ und Ga₃I₂R₃ [R = C(SiMe₃)₃] — zwei neue elementorganische Galliumsubhalogenide mit einer bzw. zwei Ga‐Ga‐Bindungen

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Pt[In-C(SiMe3)3]4 - eine zu Pt(CO)4 analoge Verbindung mit einem durch vier InR-Liganden ideal tetraedrisch koordinierten Platinatom

Cited by 41 publications

References 7 publications

Why are the Homoleptic Diyl Complexes M(InR)4 with M = Ni and Pt Stable Compounds while only Ni(CO)4 but not Pt(CO)4 can become Isolated? A Theoretical Study of M(EMe)44 and M(CO)4 (M = Ni, Pd, Pt; E = B, Al, Ga, In, Tl)

Why are the Homoleptic Diyl Complexes M(InR)4 with M = Ni and Pt Stable Compounds while only Ni(CO)4 but not Pt(CO)4 can become Isolated? A Theoretical Study of M(EMe)44 and M(CO)4 (M = Ni, Pd, Pt; E = B, Al, Ga, In, Tl)

Alkylindium Subhalides Derived from the Tetrahedral Indium(I) Cluster Compound [In4{C(SiMe3)3}4]

Ga2Br2R2 und Ga3I2R3 [R = C(SiMe3)3] — zwei neue elementorganische Galliumsubhalogenide mit einer bzw. zwei Ga‐Ga‐Bindungen

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Ga₂Br₂R₂ und Ga₃I₂R₃ [R = C(SiMe₃)₃] — zwei neue elementorganische Galliumsubhalogenide mit einer bzw. zwei Ga‐Ga‐Bindungen