Addition of Pt(PBut3) groups to Ru5(CO)12(η6-C6H6)(μ5-C).: Synthesis, structures, and dynamical activity

被引：23

作者：

Adams, RD ^{[1
]}

Captain, B

Pellechia, PJ

Zhu, L

机构：

[1] Univ S Carolina, Dept Chem & Biochem, Columbia, SC 29208 USA

[2] Univ S Carolina, USC Nanoctr, Columbia, SC 29208 USA

来源：

INORGANIC CHEMISTRY | 2004年 / 43卷 / 22期

关键词：

D O I：

10.1021/ic049004l

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

The reaction of Ru-5(CO)(12)(eta(6)-C6H6)(mu(5)-C), 7, with Pt(PBu3t)(2) yielded two products Ru-5(CO)(12)(eta(6)-C6H6)(mu(6)-C)[Pt-(PBu3t)], 8, and Ru-5(CO)(12) (eta(6)-C6H6)(mu(6)-C)[Pt(PBu3t)](2), 9. Compound 8 contains a Ru5Pt metal core in an open octahedral structure. In solution, 8 exists as a mixture of two isomers that interconvert rapidly on the NMR time scale at 20 degreesC, DeltaH(double dagger) = 7.1 (1) kcal mol(-1), DeltaS(double dagger) = -5.1(6) cal mol(-1) K-1, and DeltaG(298)(double dagger) = 8.6(3) kcal mol(-1). Compound 9 is structurally similar to 8, but has an additional Pt(PBu3t) group bridging an Ru-Ru edge of the cluster. the two Pt(PBu3t) groups in 9 rapidly exchange on the NMR time scale at 70 degreesC, DeltaH(double dagger) = 9.2(3) kcal mol(-1), DeltaS(double dagger) = -5(1) cal mol(-1) K-1, and DeltaG(298)(double dagger) = 10.7(7) kcal mol(-1). Compound 8 reacts with hydrogen to give the dihydrido complex Ru-5(CO)(11)(eta(6)-C6H6)(mu(6)-C)[Pt(PBu3t)](mu-H)(2), 10, in 59% yield. This compound consists of a closed Ru5Pt octahedron with two hydride ligands bridging two of the four Pt-Ru bonds.

引用

页码：7243 / 7249

页数：7

共 38 条

[1] High nuclearity bimetallic rhodium-palladium carbonyl cluster complexes.: Synthesis and characterization of Rh6(CO)16[Pd(PBut3)]3 and Rh6(CO)16[Pd(PBut3)]4 [J].

Adams, RD ;

Captain, B ;

Smith, MD .

JOURNAL OF CLUSTER SCIENCE, 2004, 15 (02) :139-149

[2] Dinuclear ruthenium and iron complexes containing palladium and platinum with tri-tert-butylphosphine ligands:: Synthesis, structures, and bonding [J].

Adams, RD ;

Captain, B ;

Fu, W ;

Hall, MB ;

Smith, MD ;

Webster, CE .

INORGANIC CHEMISTRY, 2004, 43 (13) :3921-3929

[3] Bimetallic cluster complexes:: The synthesis, structures, and bonding of ruthenium carbonyl cluster complexes containing palladium and platinum with the bulky tri-tert-butyl-phosphine ligand [J].

Adams, RD ;

Captain, B ;

Fu, W ;

Hall, MB ;

Manson, J ;

Smith, MD ;

Webster, CE .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2004, 126 (16) :5253-5267

[4] Platinum-rhodium carbonyl clusters: New structures and new types of dynamical activity [J].

Adams, RD ;

Captain, B ;

Pellechia, PJ ;

Smith, JL .

INORGANIC CHEMISTRY, 2004, 43 (08) :2695-2702

[5] Platinum participation in the hydrogenation of phenylacetylene by Ru5(CO)15(C)[Pt(PBu3t)] [J].

Adams, RD ;

Captain, B ;

Zhu, L .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2004, 126 (10) :3042-3043

[6] Addition of platinum and palladium tri-tert-butyl phosphine groups to open Pt-Fe and Pt-Ru metal carbonyl clusters [J].

Adams, RD ;

Captain, B ;

Fu, W ;

Smith, JL ;

Smith, MD .

ORGANOMETALLICS, 2004, 23 (03) :589-594

[7] Remarkable dynamical opening and closing of platinum and palladium pentaruthenium carbido carbonyl cluster complexes [J].

Adams, RD ;

Captain, B ;

Fu, W ;

Pellechia, PJ ;

Smith, MD .

INORGANIC CHEMISTRY, 2003, 42 (06) :2094-2101

[8] Metallation of PtRu5(CO)16(μ6-C) by using bis(tri-t-butyl-phosphine) complexes of platinum and palladium [J].

Adams, RD ;

Captain, B ;

Fu, W ;

Smith, MD .

JOURNAL OF ORGANOMETALLIC CHEMISTRY, 2003, 682 (1-2) :113-118

[9] Lewis acid-base interactions between metal atoms and their applications for the synthesis of bimetallic cluster complexes [J].

Adams, RD ;

Captain, B ;

Fu, W ;

Smith, MD .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2002, 124 (20) :5628-5629

[10]

Adams RD, 2002, ANGEW CHEM INT EDIT, V41, P1951, DOI 10.1002/1521-3773(20020603)41:11<1951::AID-ANIE1951>3.0.CO

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