Multinuclear palladium compounds containing palladium centers ligated by five silicon atoms

Shimada, Shigeru; Li, Yonghua; Choe, Yoong‐Kee; Tanaka, Masato; Bao, Ming; Uchimaru, Tadafumi

doi:10.1073/pnas.0700450104

Cited by 47 publications

(18 citation statements)

References 27 publications

(28 reference statements)

Supporting

Mentioning

Contrasting

Order By: Relevance

“…S9) and 2.6168(12)-2.8779(12) Å for III ( Supplementary Fig. S10), which are comparable to those found in previously reported polynuclear palladium clusters, including planar triangular or tetranuclear clusters [23][24][25][26][27][28][29][30][31] . Two Si atoms derived from the silylene moiety (Si(1) and Si(2)) are located on the edge of Pd 7 sheets I and III (Fig.…”

Section: Synthesis Of Folding Pd 11 Nanosheet 2 Insertion Of a Pd(cnr)supporting

confidence: 76%

A ladder polysilane as a template for folding palladium nanosheets

et al. 2013

View full text Add to dashboard Cite

Although discrete nano-sized compounds consisting of a monolayer sheet of multiple atoms have attracted much attention, monolayer transition metal nanosheets are difficult to access. Here we report a template synthesis of the folding metal nanosheet (2) consisting of 11 palladium atoms by treatment of a ladder polysilane, decaisopropylbicyclo[2.2.0]hexasilane (1), with Pd(CN t Bu) 2 . Crystallographic analysis reveals that the compound is composed of two monolayer Pd 7 sheets sharing three palladium atoms at the junction. Each Pd atom is stabilized by Pd-Si s-bonds, Pd-Pd bonds and coordination of isocyanides. Ligand exchange of 2 from CN t Bu to CN(2,4,6-Me 3 -C 6 H 2 ) is accompanied by structural rearrangement, leading to the formation of another folding Pd 11 nanosheet (3) consisting of two edge-sharing Pd 7 sheets. The shapes of the Pd 7 sheets as well as the dihedral angle between the two Pd 7 sheets are dependent on the substituent of the isocyanide ligand.

show abstract

Section: Synthesis Of Folding Pd 11 Nanosheet 2 Insertion Of a Pd(cnr)supporting

confidence: 76%

A ladder polysilane as a template for folding palladium nanosheets

et al. 2013

View full text Add to dashboard Cite

show abstract

“…The Pd(3)-Pd(4) bond length (2.7523(5) Å) is slightly longer than Pd(1)-Pd(4) (2.6812(6) Å) and Pd(2)-Pd(4) (2.6778(6) Å); however, they are within the range of metal-metal bonding interaction reported in the literature [10]. [35][36][37][38][39]. This difference may be derived from the formal electron configurations of Pd (1) and Pd (2).…”

Section: Synthesis Of Planar Pd4 Cluster 4 By Reaction Of Pd(cn T Bu)mentioning

confidence: 43%

“…The bond distances of Pd(1)-Si(1) and Pd(2)-Si(1) are 2.4252(12) and 2.4339(12) Å, respectively, which are considerably shorter than those observed in other Pd(edge)-Si moieties (2.5094(11)-2.6401(12) Å). In contrast, the Pd(edge)-Si(silylene) bond distances in Osakada's Pd 4 Si 3 cluster are reported to be 2.505-2.546 Å with no significant deviation [35][36][37][38][39]. This difference may be derived from the formal electron configurations of Pd (1) and Pd (2).…”

Section: Synthesis Of Planar Pd4 Cluster 4 By Reaction Of Pd(cn T Bu)mentioning

confidence: 56%

Construction of a Planar Tetrapalladium Cluster by the Reaction of Palladium(0) Bis(isocyanide) with Cyclic Tetrasilane

et al. 2017

View full text Add to dashboard Cite

Abstract:The planar tetrapalladium cluster Pd 4 {Si( i Pr) 2 } 3 (CN t Bu) 4 (4) was synthesised in 86% isolated yield by the reaction of palladium(0) bis(isocyanide) Pd(CN t Bu) 2 with octaisopropylcyclotetrasilane (3). In the course of this reaction, the palladium atoms are clustered via insertion into the Si-Si bonds of 3, followed by extrusion of one Si i Pr 2 moiety and reorganisation to afford 4 with a 54-electron configuration. The CN t Bu ligand in 4 was found to be easily replaced by N-heterocyclic carbene ( i Pr 2 IM Me ) to afford the more coordinatively unsaturated cluster Pd 4 {Si( i Pr) 2 } 3 ( i Pr 2 IM Me ) 3 (5) having the planar Pd 4 Si 3 core. On the other hand, the replacement of CN t Bu with a sterically compact ligand trimethylolpropane phosphite {P(OCH 2 ) 3 CEt} led to a planar tripalladium cluster Pd 3 {Si( i Pr) 2 } 3 {P(OCH 2 ) 3 CEt} 3 (6) and Pd{P(OCH 2 ) 3 CEt} 4 in 1:1 molar ratio as products.

show abstract

“…[4a] Shimada and coworkers have recently described a multinuclear complex containing a {Pd 4 Si 5 } framework composed of a planar Pd 4 Si 3 core, similar to 2, and two additional Si ligands at the central Pd atom. [20] The Pd cent À Si bond lengths of the {Pd 4 Si 3 } plane (2.3265 (13) and 2.2944 (9) ) are significantly longer than the corresponding bonds in 2.…”

mentioning

confidence: 98%

Planar Tetranuclear and Dumbbell‐Shaped Octanuclear Palladium Complexes with Bridging Silylene Ligands

et al. 2008

View full text Add to dashboard Cite

Late-transition-metal complexes with silylene (SiR 2 ) ligands have attracted considerable attention since the proposal of platinum-silylene intermediates in the [PtCl 2 (PEt 3 ) 2 ]-catalyzed reactions that convert organodisilanes into oligosilanes and the cyclic adducts into alkynes.[1] Mononuclear silylene complexes of platinum [2] and other late transition metals [3] were not isolated until some years later, probably because of the extremely high reactivity of most M = Si double bonds. Dinuclear complexes of late transition metals with bridging silylene ligands are more common.[4] The dinuclear platinum complex [{Pt(PR 3 )} 2 (m-SiHPh 2 ) 2 ] (PR 3 = PPh 3 , PCy 3 etc.) has been reported.[5] However, in spite of the stable coordination of bridging silylene ligands, complexes containing three or more metal atoms with bridging Si ligands have few precedents, [6] and those known are stabilized by electron-withdrawing CO and CNR ligands.[7] Braddock-Wilking and coworkers [8] and our group [9,10] have reported zero-valent triangular Pt 3 complexes, stabilized by bridging silylene and phosphine ligands. Chen, Shimada, and Tanaka employed 1,2-disilabenzene as a ligand and prepared trinuclear Pd complexes supported by the Si ligands.[11]Herein, we report the synthesis and unexpected structure of a planar tetranuclear Pd 0 complex with three bridging SiPh 2 ligands as well as facile exchange of the bridging silylene ligands to yield a dumbbell-shaped octapalladium complex composed of two Pd 4 units bridged by a diphosphine ligand. These complexes, composed of Pd 0 centers and electrondonating Si and phosphine ligands, possess a unique planar {Pd 4 Si 3 } core.Heating a mixture of a dipalladium complex with bridging diphenylsilyl ligands, [{Pd(PCy 3 )} 2 (m-h 2 -SiHPh 2 ) 2 ] (1), [12] The molecular structure of 2 was determined by singlecrystal X-ray diffraction (Figure 1). [14] Complex 2 has a hexagonal {Pd 4 Si 3 } core incorporating one central Pd atom,

show abstract

Multinuclear palladium compounds containing palladium centers ligated by five silicon atoms

Cited by 47 publications

References 27 publications

A ladder polysilane as a template for folding palladium nanosheets

A ladder polysilane as a template for folding palladium nanosheets

Construction of a Planar Tetrapalladium Cluster by the Reaction of Palladium(0) Bis(isocyanide) with Cyclic Tetrasilane

Planar Tetranuclear and Dumbbell‐Shaped Octanuclear Palladium Complexes with Bridging Silylene Ligands

Contact Info

Product

Resources

About