11. Binuclear Transition Metal Complexes Bridged by Methylenebis(Diphenylphosphine)

Balch, Alan L.; Benner, Linda S.; Basil, John D.

doi:10.1002/9780470132524.ch11

Cited by 19 publications

(1 citation statement)

References 9 publications

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“…Materials. Pd 2 (dppm) 2 Cl 2 , Pt 2 (dppm) 2 Cl 2 , [Pd 2 (dppm) 2 (NCCH 3 ) 2 ](PF 6 ) 2 , [Pt 2 (dppm) 2 (NCCH 3 ) 2 ](PF 6 ) 2 , [Pt 2 (dppm) 2 (2,5-CNC 6 Me 2 H 3 ) 2 ](BF 4 ) 2 , 1-isocyano-2,5-dimethylbenzene, 4-diisocyano-2,3,5,6-tetramethylbenzene, 1,8-diisocyano-p-menthane, 1-isocyano-2,6-dimethylbenzene, and 1-isocyano-4-isopropylbenzene 9 were prepared according to standard procedures. The following materials were purchased from commercial suppliers: dppm (Aldrich), t -Bu-NC (Aldrich), PdCl 2 (Pressure Chemical), K 2 PtCl 4 (Strem), acetone (Fisher), acetonitrile, petroleum ether, dichloromethane (ACP), ethanol (Les Alcools de Commerce Inc.), PrCN (Aldrich), dinitrogen, and argon (Praxair).…”

Section: Methodsmentioning

confidence: 99%

Solution and Solid-State Properties of Luminescent M−M Bond-Containing Coordination/Organometallic Polymers Using the RNC-M₂(dppm)₂-CNR Building Blocks (M = Pd, Pt; R = Aryl, Alkyl)

et al. 2006

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Two families of organometallic polymers built upon the bimetallic M2(dppm)2L(2)2+ fragments (M = Pd, Pt; dppm = bis(diphenylphosphino)methane, L = 1,4-diisocyano-2,3,5,6-tetramethylbenzene (diiso), 1,8-diisocyano-p-menthane (dmb), 1-isocyano-2,6-dimethylbenzene, 1-isocyano-4-isopropylbenzene, and tert-butylisocyanide) were synthesized and fully characterized (1H and 31P NMR, X-ray crystallography (model compounds), IR, Raman, chem. anal., TGA, DSC, powder XRD, 31P NMR T1 and NOE, light scattering, and conductivity measurements). Evidence for polymers in the solid state is provided from the swelling of the polymers upon dissolution and the formation of stand-alone films. However, these species become small oligomers when dissolved. The materials are luminescent in the solid state at 298 and 77 K and in PrCN solution at 77 K. These emissions result from triplet 3(d sigma d sigma*) states despite the presence of low-lying pi-pi* MO levels according to DFT calculations for the aryl isocyanide model compounds. The emission band maxima are located between 640 and 750 nm and exhibit lifetimes of 3-6 ns for the Pd species and 3-4 micros for the Pt analogues in PrCN solution at 77 K. No evidence of intramolecular excitonic photoprocesses was found in any of the polymers.

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Section: Methodsmentioning

confidence: 99%

Solution and Solid-State Properties of Luminescent M−M Bond-Containing Coordination/Organometallic Polymers Using the RNC-M₂(dppm)₂-CNR Building Blocks (M = Pd, Pt; R = Aryl, Alkyl)

et al. 2006

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Sterically Controlled Pathways in the Reaction of 2,4,6-Tris(isopropyl)benzenesulfonyl Azide and [Pd2Cl2(dppm)2]

Besenyei¹,

Pa̋rkányi²,

Foch³

et al. 2000

Angewandte Chemie

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Organic azides often react with metal complexes with extrusion of N 2 , affording imido (nitrene) derivatives. [1] The azide moiety is not necessarily cleaved, however, as illustrated by earlier studies on hydridoosmium and dimeric molybdenum complexes. [2] Several aryl and cyclohexyl azide complexes revealing various modes of coordination have recently been characterized structurally and chemically. [3] Our previous work on the phosgene-free synthesis of isocyanates has shown that arenesulfonyl azides react with [Pd 2 Cl 2 (dppm) 2 ] (1, dppm bis(diphenylphosphanyl)methane), resulting in the formation of arylsulfonylimido A-frame adducts. [4,5] These novel reactions show good selectivities with most sulfonyl azides, except for the 2-nitro derivative, which gave [Pd 2 Cl 2 (dppm) 2 (N 3 SO 2 C 6 H 4 -2-NO 2 )] as a by-product. [5a] To elucidate the steric effects of azide ligands, we conducted studies with 2,4,6-tris(isopropyl)benzenesulfonyl azide (TipSO 2 N 3 , 2). The results of these investigations, together with crystallographic data on the parent azide 2, are presented here.Reaction of [Pd 2 Cl 2 (dppm) 2 ] with 2 affords the azide complex 3 and the nitrene complex 4 in 75 and 25 % yield, respectively [Eq. (1); 1 H NMR, see the Experimental Section], involving a very bulky bridging imido ligand. The 2 [Pd 2 Cl 2 (dppm) 2 ] 2 TipSO 2 N 3 ÀN2 3 1 2 [Pd 2 Cl 2 (dppm) 2 (m,h 1 -N 3 SO 2 Tip)] [Pd 2 Cl 2 (dppm) 2 (m-NSO 2 Tip)](1)3 4 molecular structures of the complexes formed are shown in Figures 1 and 2. The products are typical A-frame adducts with an extended boat conformation of the Pd 2 P 4 C 2 ring. The PdÀPd distances are about 0.6 longer than in [Pd 2 Br 2 (dppm) 2 ], ruling out metal ± metal bonding. [6] The redistribution of valence electrons induced by coordination can be best visualized by comparing bond lengths in free and coordinated sulfonyl azide. Although N3 is disordered in 2 (structure not shown, the numbering corresponds to that of 3), the short N1ÀN2 and N2ÀN3 bonds (1.213(3) and 1.14 ) indicate multiple bonding, in line with structural data for other sulfonyl azides. [7] Decreased bond orders as a result of complexation are clear from the N2ÀN3 and N1ÀN2 distances of 1.248(5) and 1.340(5) in 3. The structural features of 3 are consistent with 2 reacting as a 1,3-dipole (ArÀSO 2 ÀN À ÀNN ), producing a zwitterionic structure with the negative charge delocalized on the N1ÀN2 and N1ÀS1 bonds. The azide-to-sulfonyl electron transfer shortens the Figure 1. Molecular structure of 3 without hydrogen atoms. Selected interatomic distances [] and angles [8]:

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Assembling Ligand Substitution Reactions Monitored by VT 31P{H} NMR Spectroscopy In Order to Shine Light on the Mechanism of Formation of the Pd–Pd Bond-Containing {Pd2 (dmb)2(diphos)2+} n , {Pd2(diphos′)2 (dmb)2+} n and {Pd2 (dppm)2 (diphos)2+} n Coordination/Organometallic Polymers

Samar

Harvey

2007

J Inorg Organomet Polym

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11. Binuclear Transition Metal Complexes Bridged by Methylenebis(Diphenylphosphine)

Cited by 19 publications

References 9 publications

Solution and Solid-State Properties of Luminescent M−M Bond-Containing Coordination/Organometallic Polymers Using the RNC-M₂(dppm)₂-CNR Building Blocks (M = Pd, Pt; R = Aryl, Alkyl)

Solution and Solid-State Properties of Luminescent M−M Bond-Containing Coordination/Organometallic Polymers Using the RNC-M₂(dppm)₂-CNR Building Blocks (M = Pd, Pt; R = Aryl, Alkyl)

Sterically Controlled Pathways in the Reaction of 2,4,6-Tris(isopropyl)benzenesulfonyl Azide and [Pd2Cl2(dppm)2]

Assembling Ligand Substitution Reactions Monitored by VT 31P{H} NMR Spectroscopy In Order to Shine Light on the Mechanism of Formation of the Pd–Pd Bond-Containing {Pd2 (dmb)2(diphos)2+} n , {Pd2(diphos′)2 (dmb)2+} n and {Pd2 (dppm)2 (diphos)2+} n Coordination/Organometallic Polymers

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11. Binuclear Transition Metal Complexes Bridged by Methylenebis(Diphenylphosphine)

Cited by 19 publications

References 9 publications

Solution and Solid-State Properties of Luminescent M−M Bond-Containing Coordination/Organometallic Polymers Using the RNC-M2(dppm)2-CNR Building Blocks (M = Pd, Pt; R = Aryl, Alkyl)

Solution and Solid-State Properties of Luminescent M−M Bond-Containing Coordination/Organometallic Polymers Using the RNC-M2(dppm)2-CNR Building Blocks (M = Pd, Pt; R = Aryl, Alkyl)

Sterically Controlled Pathways in the Reaction of 2,4,6-Tris(isopropyl)benzenesulfonyl Azide and [Pd2Cl2(dppm)2]

Assembling Ligand Substitution Reactions Monitored by VT 31P{H} NMR Spectroscopy In Order to Shine Light on the Mechanism of Formation of the Pd–Pd Bond-Containing {Pd2 (dmb)2(diphos)2+} n , {Pd2(diphos′)2 (dmb)2+} n and {Pd2 (dppm)2 (diphos)2+} n Coordination/Organometallic Polymers

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Solution and Solid-State Properties of Luminescent M−M Bond-Containing Coordination/Organometallic Polymers Using the RNC-M₂(dppm)₂-CNR Building Blocks (M = Pd, Pt; R = Aryl, Alkyl)

Solution and Solid-State Properties of Luminescent M−M Bond-Containing Coordination/Organometallic Polymers Using the RNC-M₂(dppm)₂-CNR Building Blocks (M = Pd, Pt; R = Aryl, Alkyl)