Control of the Bridgehead Donor Atom in the Tripodal Ligand over Oxidative Addition of Au(PPh3)+ to [X(CH2CH2PPh2)3RhH] (X = N, P). X-ray Diffraction and Multinuclear (103Rh, 31P, 1H) NMR Studies

Bianchini, Claudio; Elsevier, Cornelis J.; Ernsting, Jan Meine; Peruzzini, Maurizio; Zanobini, Fabrizio

doi:10.1021/ic00105a017

Cited by 26 publications

(14 citation statements)

References 11 publications

(13 reference statements)

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“…All complexes of PP 3 involving metal-metal bonds reported so far (Scheme 2) involve this bonding mode. [2][3][4][5] We report here on the facile formation of dinuclear metalmetal bonded M 2 (µ-PP 3 -P,PЈ : PЉ,Pٞ) fragments depicted in Scheme 1.…”

Section: Introductionmentioning

confidence: 99%

P(CH2CH2PPh2)3 Bridged Group 10 dimetal centres

Wachtler

Schuh

Ongania

et al. 2002

J. Chem. Soc., Dalton Trans.

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Section: Introductionmentioning

confidence: 99%

P(CH2CH2PPh2)3 Bridged Group 10 dimetal centres

Wachtler

Schuh

Ongania

et al. 2002

J. Chem. Soc., Dalton Trans.

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“…In this case, stable complexes of type II have been isolated and characterized in numerous occasions. [11][12][13][14][15][16][17][18][19][20][21][22][23][24] Whenever these adducts are not stable, the † Current address: Laboratoire de Synthe `se et d'Electrosynthe `se Organometallique, Faculte ´des Sciences "Gabriel", 6 Boulevard Gabriel, 21100 Dijon, France.…”

Section: Introductionmentioning

confidence: 99%

H⁺/AuPPh₃⁺Exchange for the Hydride Complexes CpMoH(CO)₂(L) (L = PMe₃, PPh₃, CO). Formation and Structure of [Cp(CO)₂(PMe₃)Mo(AuPPh₃)₂]⁺[BF₄]^-

et al. 1997

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The reaction of CpMoH(CO)(2)L with AuPPh(3)(+)BF(4)(-) in THF at -40 degrees C proceeds directly to the MoAu(2) cluster compounds [CpMo(CO)(2)L(AuPPh(3))(2)](+)BF(4)(-) (L = PMe(3) (1), PPh(3) (2)) with release of protons. A 1:1 reaction leaves 50% of the starting hydride unreacted. At lower temperature, however, the formation of a [CpMo(CO)(2)(PMe(3))(&mgr;-H)(AuPPh(3))](+) intermediate is observed. This compound evolves to the cation of 1 and CpMoH(CO)(2)(PMe(3)) upon warming and is deprotonated by 2,6-lutidine to afford CpMo(CO)(2)(PMe(3))(AuPPh(3)). The X-ray structure of 1 can be described as a four-legged piano stool with the PMe(3) and the "eta(2)-(AuPPh(3))(2)" ligands occupying relative trans positions. [Cp(CO)(2)(PMe(3))Mo(AuPPh(3))(2)](+)[BF(4)](-) (M(r) = 1298.41): monoclinic, space group P2(1)/n, a = 18.1457(13) Å, b = 9.7811(7) Å, c = 26.096(2) Å, beta = 105.086(5) degrees, V = 4472.0(5) Å(3), Z = 4. The reaction of CpMoH(CO)(2)(PMe(3)) with 3 equiv of AuPPh(3)(+) affords a MoAu(3) cluster, [CpMo(CO)(2)(PMe(3))(AuPPh(3))(3)](2+) (3), in good yields under kinetically controlled conditions. Under thermodynamically controlled conditions, 3 dissociates extensively into 1 and free AuPPh(3)(+). It is proposed that the hydride ligand helps build higher nuclearity Mo-Au clusters. The difference in reaction pathways for the interaction of AuPPh(3)(+) with CpMoH(CO)(2)L when L = PR(3) or CO and for the interaction of CpMoH(CO)(2)(PMe(3)) with E(+) when E = H, Ph(3)C or AuPPh(3) is discussed. The lower acidity and greater aurophilicity of the [CpMo(CO)(2)L(&mgr;-H)(AuPPh(3))](+) intermediate when L = PMe(3) favor attack by AuPPh(3)(+) before deprotonation.

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“…As expected, the rhodium center in the two structures adopts a piano‐stool conformation. Compound 3 b exhibits a Rh‐Au bond distance of 2.593(1) Å, comparable to the only other example of a bimetallic Rh/Au unsupported MOLP of this kind [26] . This value is shortened by around 0.2 Å with respect to the sum of their covalent radii (2.78 Å), [27] thus providing support for the existence of a dative Rh→Au bond.…”

Section: Figurementioning

confidence: 59%

“…Compound 3 b exhibits a Rh-Au bond distance of 2.593(1) , comparable to the only other example of a bimetallic Rh/Au unsupported MOLP of this kind. [26] This value is shortened by around 0.2 with respect to the sum of their covalent radii (2.78 ), [27] thus providing support for the existence of a dative Rh!Au bond. Similarly, the calculated formal shortness ratio (FSR), [28] defined as the ratio between the MÀM length and the sum of metallic radii, exactly accounts for 1.00.…”

mentioning

confidence: 90%

Reversible Hydride Migration from C₅Me₅ to Rh^I Revealed by a Cooperative Bimetallic Approach

et al. 2020

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The use of cyclopentadienyl ligands in organometallic chemistry and catalysis is ubiquitous, mostly due to their robust spectator role. Nonetheless, increasing examples of non‐innocent behaviour are being documented. Here, we provide evidence for reversible intramolecular C−H activation at one methyl terminus of C5Me5 in [(η‐C5Me5)Rh(PMe3)2] to form a new Rh−H bond, a process so far restricted to early transition metals. Experimental evidence was acquired from bimetallic rhodium/gold structures in which the gold center binds either to the rhodium atom or to the activated Cp* ring. Reversibility of the C−H activation event regenerates the RhI and AuI monometallic precursors, whose cooperative reactivity towards polar E−H bonds (E=O, N), including the N−H bonds in ammonia, can be understood in terms of bimetallic frustration.

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Control of the Bridgehead Donor Atom in the Tripodal Ligand over Oxidative Addition of Au(PPh3)+ to [X(CH2CH2PPh2)3RhH] (X = N, P). X-ray Diffraction and Multinuclear (103Rh, 31P, 1H) NMR Studies

Cited by 26 publications

References 11 publications

P(CH2CH2PPh2)3 Bridged Group 10 dimetal centres

P(CH2CH2PPh2)3 Bridged Group 10 dimetal centres

H⁺/AuPPh₃⁺Exchange for the Hydride Complexes CpMoH(CO)₂(L) (L = PMe₃, PPh₃, CO). Formation and Structure of [Cp(CO)₂(PMe₃)Mo(AuPPh₃)₂]⁺[BF₄]^-

Reversible Hydride Migration from C₅Me₅ to Rh^I Revealed by a Cooperative Bimetallic Approach

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Control of the Bridgehead Donor Atom in the Tripodal Ligand over Oxidative Addition of Au(PPh3)+ to [X(CH2CH2PPh2)3RhH] (X = N, P). X-ray Diffraction and Multinuclear (103Rh, 31P, 1H) NMR Studies

Cited by 26 publications

References 11 publications

P(CH2CH2PPh2)3 Bridged Group 10 dimetal centres

P(CH2CH2PPh2)3 Bridged Group 10 dimetal centres

H+/AuPPh3+Exchange for the Hydride Complexes CpMoH(CO)2(L) (L = PMe3, PPh3, CO). Formation and Structure of [Cp(CO)2(PMe3)Mo(AuPPh3)2]+[BF4]-

Reversible Hydride Migration from C5Me5 to RhI Revealed by a Cooperative Bimetallic Approach

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H⁺/AuPPh₃⁺Exchange for the Hydride Complexes CpMoH(CO)₂(L) (L = PMe₃, PPh₃, CO). Formation and Structure of [Cp(CO)₂(PMe₃)Mo(AuPPh₃)₂]⁺[BF₄]^-

Reversible Hydride Migration from C₅Me₅ to Rh^I Revealed by a Cooperative Bimetallic Approach