Complexation of tin(II) chloride by a novel macrocycle containing rhodium and nitrogen binding sites. The preparation and x-ray crystal structure of Rh2Sn2(CO)2Cl6[.mu.-2,6-bis(diphenylphosphino)pyridine]2

Balch, Alan L.; Hope, H.; Wood, Fred E.

doi:10.1021/ja00310a032

Cited by 51 publications

(16 citation statements)

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“…Another possibility, albeit much less common, is the insertion of a main-group metal such as tin into TM-halogen bonds, which does not affect the oxidation state of the TM. [8][9][10][11] In the present work we focus on the combination of these two reaction patterns, that is, the insertion of a TM into a TM-halogen bond; this constitutes a versatile route to heterodinuclear TM complexes containing platinum and a coinage metal.There have been numerous investigations into the bonding properties of homo-and heterodinuclear transition-metal complexes. Among the earliest examples were homodinuclear complexes consisting of d 8 -d 8 as well as d 10 -d 10 systems (type B, Figure 1).…”

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Reversible Insertion of Platinum into Coinage Group Metal–Halogen Bonds

et al. 2012

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Insertion of transition-metal (TM) complexes into elementhalogen bonds is one of the basic concepts in TM chemistry. The most common examples are found for main-group species such as alkyl [1][2][3] and boryl halides. [4][5][6][7] Here, the insertion proceeds with oxidation of the TM and thus constitutes an oxidative addition (OA) process, which is a crucial step in TM-mediated catalysis. Another possibility, albeit much less common, is the insertion of a main-group metal such as tin into TM-halogen bonds, which does not affect the oxidation state of the TM. [8][9][10][11] In the present work we focus on the combination of these two reaction patterns, that is, the insertion of a TM into a TM-halogen bond; this constitutes a versatile route to heterodinuclear TM complexes containing platinum and a coinage metal.There have been numerous investigations into the bonding properties of homo-and heterodinuclear transition-metal complexes. Among the earliest examples were homodinuclear complexes consisting of d 8 -d 8 as well as d 10 -d 10 systems (type B, Figure 1). [12][13][14][15] However, the combination of plati-num and gold is exclusively found in mixed-valence systems, such as d 8 -d 10 (type A) and d 7 -d 9 ; [16][17][18][19] in contrast, the route presented herein leads to heterodinuclear d 10 -d 10 complexes. In addition, the most striking feature of nearly all known compounds of this type is the chelating ligand forcing the two transition metals to interact. Again this stands in stark contrast to the compounds presented in this work that contain unsupported TM-TM bonds without a bridging ligand.While unsupported bonds are relatively uncommon, [20] a few examples of complexes having d 8 -d 10 interactions should be mentioned (type C). [21] To the best of our knowledge, the only complex featuring an unsupported d 10 -d 10 interaction (type D) between platinum and a coinage-group metal was reported by Sharp et al. in 1998. [22] However, no signs of an insertion reaction were detected at that time.In contrast, in our synthetic approach we use the wellestablished transition-metal Lewis base [(Cy 3 P) 2 Pt] (1) and the gold complex [(Cy 3 P)AuCl] (2). We describe the unprecedented reversible insertion of the Lewis basic platinum fragment into a coinage-metal-halogen bond. The insertion products were investigated by multinuclear NMR spectroscopy and single-crystal X-ray diffraction. In addition, we present a possible mechanism for the insertion reaction supported by density functional calculations.The reaction of the sterically and electronically unsaturated platinum compound [(Cy 3 P) 2 Pt] (1) with an equimolar amount of [(Cy 3 P)AuCl] (2) leads instantly to an equilibrium of the two starting materials with a new complex 3, as indicated by 31 P{ 1 H} NMR spectroscopic data. The resonances of 1 (d = 62.2 ppm), flanked by 195 Pt satellites (J = 4155 Hz), and 2 (d = 53.1 ppm) are accompanied by the resonances of 3 at d = 42.7 ppm (J = 3157 Hz) and d = 38.2 ppm (J = 1295 Hz). The appearance of 195 Pt satellites in bo...

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Reversible Insertion of Platinum into Coinage Group Metal–Halogen Bonds

et al. 2012

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“…M 0 bond between an electron-rich metal M and a high oxidation-state metal M 0n+ . Since the coordination chemistry of Ph 2 Ppy was first developed by Balch et al [11][12][13], a lot of studies have been done by several groups. For example, Cotton et al [14], Faraone et al [15] and Zhang et al [16,17,7] have synthesized various novel binuclear complexes involving almost all metal atoms in VIB, VIIB, VIIIB, IB, IIB groups such as palladium, platinum, ruthenium, rhodium, iridium, silver, gold, copper, rhenium, molybdenum, etc.…”

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confidence: 99%

Quantum chemistry studies on the Ru–M interactions and the 31P NMR in [Ru(CO)3(Ph2Ppy)2(MCl2)] (M=Zn, Cd, Hg)

Fang

Chen

et al. 2006

Journal of Organometallic Chemistry

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“…[7] The yellow colour is indicative of square-planar, noninteracting rhodium centres. [8] Macrocycles of similar types, for example [Rh 2 Cl 2 (CO) 2 {µ-(Ph 2 P) 2 py} 2 ] [9] and [Rh 2 (CO) 2 Cl 2 {Ph 2 P(CH 2 )P(S)Ph 2 } 2 ], [7] have been reported previously for rhodium but never used as catalysts.…”

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confidence: 98%