Preparation and reactions of the (pentamethylcyclopentadienyl)rhodium(III) complexes bearing 1,1′-bis(diphenylphosphinomethyl)ferrocene (dpmf) or 1,1′-bis(diphenylphosphino)ferrocene (dppf)

Ma, Jian-Fang; Yamamoto, Yasuhiro

doi:10.1016/s0022-328x(98)00939-5

Cited by 22 publications

(18 citation statements)

References 13 publications

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“…The data provide a reasonable estimated Rh-H distance of 1.42(12)/1.46(12) Å [25] with the caveat that the presence of the electron-rich rhodium could lead to underestimation of the Rh-H distance. [26] As has been observed in prior structures of dppf bound to rhodium, [13,27] the cyclopentadienyl rings within dppf were found to be canted slightly toward the Rh center in 4, with 6.5º/3.0º between their mean planes [25] in the two molecular cations found in the unit cell of the structure of 4. We have previously found that diphosphine-supported [Cp*Rh] monohydrides are not readily protonolyzed by the strong acid dimethylformamidinium (denoted [DMFH] + ; pK a = 6.1 in MeCN [23] ) when they are in the formal rhodium(III) oxidation state.…”

Section: Resultsmentioning

confidence: 53%

“…The synthesis, spectroscopic characterization, and X-ray diffraction structure of the [Cp*Rh(dppf)Cl] + (1; see Scheme 1) have been previously reported. [13] However, the electrochemical properties of 1 were not investigated in the prior work. Cyclic voltammetric investigation of 1 at oxidizing potentials reveals a single quasi-reversible couple centered at +0.38 V vs. the ferrocenium/ferrocene couple (denoted hereafter as Fc +/0 ) with a peak-to-peak separation (ΔE p ) of 158 mV typical of 1ecouples in THF (see Figure 1).…”

Section: Resultsmentioning

confidence: 99%

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Remote Oxidative Activation of a [Cp*Rh] Monohydride**

Boyd

Leseberg

Cosner

et al. 2022

Chemistry A European J

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Half-sandwich rhodium monohydrides are often proposed as intermediates in catalysis, but little is known regarding the redox-induced reactivity accessible to these species. Here, the κ 2bis-diphenylphosphinoferrocene (dppf) ligand has been used to explore the reactivity that can be induced when a [Cp*Rh] monohydride undergoes remote (dppf-centered) oxidation by 1e -. Chemical and electrochemical studies showed that one-electron redox chemistry is accessible to Cp*Rh(dppf), including a unique quasi-reversible Rh II/I process at -0.96 V vs. ferrocenium/ferrocene (Fc +/0 ). This redox manifold was confirmed by isolation of an uncommon Rh(II) species that was characterized by EPR spectroscopy. Protonation of Cp*Rh(dppf) with anilinium triflate yielded an isolable and inert monohydride, and this species was found to undergo a quasireversible electrochemical oxidation at +0.41 V vs Fc +/0 that corresponds to iron-centered oxidation in the dppf backbone. Thermochemical analysis predicts that this dppf-centered oxidation drives a dramatic increase in acidity of the Rh-H moiety by 23 pK a units, a reactivity pattern confirmed by in situ 1 H NMR studies. Taken together, these results show that remote oxidation can effectively induce M-H activation and suggest that ligand-centered redox activity could be an attractive feature for design of new systems relying on hydride intermediates.

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Section: Resultsmentioning

confidence: 53%

Section: Resultsmentioning

confidence: 99%

Remote Oxidative Activation of a [Cp*Rh] Monohydride**

Boyd

Leseberg

Cosner

et al. 2022

Chemistry A European J

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“…LiPMe 2 Á 0.5Et 2 O was prepared by deprotonating HPMe 2 using a modification of IssleibÕs method [22] with t BuLi was used as the base instead of PhLi. The reagents LiPPh 2 [23], [Fe(g 5 -C 5 H 4 SiMe 2 Cl) 2 ] [24], and (nbd)Mo(CO) 4 [25] were prepared using published procedures. (1) 1,1 0 -Bis(chlorodimethylsilyl)ferrocene (1.86 g, 5.0 mmol) was dissolved in Et 2 O (40 ml).…”

Section: Compoundmentioning

confidence: 99%

“…However, less attention has focused on synthesising ligands containing a group between the ferrocene cyclopentadienyl ring and the phosphorus atoms. Bidentate ferrocene diphosphane ligands containing a carbon spacer have been prepared and studied by us and others [9][10][11]. Herein, we report the synthesis and properties of ferrocenyl phosphane ligands with a silyl spacer.…”

Section: Introductionmentioning

confidence: 97%

“…The most common ligand in this class is 1,1 0 -bis(diphenylphosphino)ferrocene (dppf). The dppf ligand has been coordinated to most late transition metals [2] and complexes of this ligand have been used in a range of catalytic reactions including carbon-carbon coupling [3,4] and hydroformylation reactions [5]. Transition metals containing ferrocene-based ligands, such as dppf, often show superior catalytic activity when compared to complexes containing other types of bidentate diphosphane ligands [6].…”

Section: Introductionmentioning

confidence: 99%

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Silicon containing ferrocenyl phosphane ligands

Coleman

Turberville

Pascu

et al. 2004

Journal of Organometallic Chemistry

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Mixed‐Transition‐Metal Acetylides: Synthesis and Characterization of Complexes with up to Six Different Transition Metals Connected by Carbon‐Rich Bridging Units

Packheiser

Ecorchard

Rüffer

et al. 2008

Chemistry A European J

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The synthesis and reaction chemistry of heteromultimetallic transition-metal complexes by linking diverse metal-complex building blocks with multifunctional carbon-rich alkynyl-, benzene-, and bipyridyl-based bridging units is discussed. In context with this background, the preparation of [1-{(eta(2)-dppf)(eta(5)-C(5)H(5))RuC[triple bond]C}-3-{(tBu(2)bpy)(CO)(3)ReC[triple bond]C}-5-(PPh(2))C(6)H(3)] (10) (dppf = 1,1'-bis(diphenylphosphino)ferrocene; tBu(2)bpy = 4,4'-di-tert-butyl-2,2'-bipyridyl; Ph = phenyl) is described; this complex can react further, leading to the successful synthesis of heterometallic complexes of higher nuclearity. Heterotetrametallic transition-metal compounds were formed when 10 was reacted with [{(eta(5)-C(5)Me(5))RhCl(2)}(2)] (18), [(Et(2)S)(2)PtCl(2)] (20) or [(tht)AuC[triple bond]C-bpy] (24) (Me = methyl; Et = ethyl; tht = tetrahydrothiophene; bpy = 2,2'-bipyridyl-5-yl). Complexes [1-{(eta(2)-dppf)(eta(5)-C(5)H(5))RuC[triple bond]C}-3-{(tBu(2)bpy)(CO)(3)ReC[triple bond]C}-5-{PPh(2)RhCl(2)(eta(5)-C(5)Me(5))}C(6)H(3)] (19), [{1-[(eta(2)-dppf)(eta(5)-C(5)H(5))RuC[triple bond]C]-3-[(tBu(2)bpy)(CO)(3)ReC[triple bond]C]-5-(PPh(2))C(6)H(3)}(2)PtCl(2)] (21), and [1-{(eta(2)-dppf)(eta(5)-C(5)H(5))RuC[triple bond]C}-3-{(tBu(2)bpy)(CO)(3)ReC[triple bond]C}-5-{PPh(2)AuC[triple bond]C-bpy}C(6)H(3)] (25) were thereby obtained in good yield. After a prolonged time in solution, complex 25 undergoes a transmetallation reaction to produce [(tBu(2)bpy)(CO)(3)ReC[triple bond]C-bpy] (26). Moreover, the bipyridyl building block in 25 allowed the synthesis of Fe-Ru-Re-Au-Mo- (28) and Fe-Ru-Re-Au-Cu-Ti-based (30) assemblies on addition of [(nbd)Mo(CO)(4)] (27), (nbd = 1,5-norbornadiene), or [{[Ti](mu-sigma,pi-C[triple bond]CSiMe(3))(2)}Cu(N[triple bond]CMe)][PF(6)] (29) ([Ti] = (eta(5)-C(5)H(4)SiMe(3))(2)Ti) to 25. The identities of 5, 6, 8, 10-12, 14-16, 19, 21, 25, 26, 28, and 30 have been confirmed by elemental analysis and IR, (1)H, (13)C{(1)H}, and (31)P{(1)H} NMR spectroscopy. From selected samples ESI-TOF mass spectra were measured. The solid-state structures of 8, 12, 19 and 26 were additionally solved by single-crystal X-ray structure analysis, confirming the structural assignment made from spectroscopy.

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Preparation and reactions of the (pentamethylcyclopentadienyl)rhodium(III) complexes bearing 1,1′-bis(diphenylphosphinomethyl)ferrocene (dpmf) or 1,1′-bis(diphenylphosphino)ferrocene (dppf)

Cited by 22 publications

References 13 publications

Remote Oxidative Activation of a [Cp*Rh] Monohydride**

Remote Oxidative Activation of a [Cp*Rh] Monohydride**

Silicon containing ferrocenyl phosphane ligands

Mixed‐Transition‐Metal Acetylides: Synthesis and Characterization of Complexes with up to Six Different Transition Metals Connected by Carbon‐Rich Bridging Units

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