[8,8-η2-{η2-(BH3)Ph2PCH2PPh2}-nido-8,7-RhSB9H10]: A Rhodathiaborane with a Novel Bidentate Chelating Ligand

Macı́as, Ramón; Rath, Nigam P.; Barton, Lawrence

doi:10.1002/(sici)1521-3773(19990115)38:1/2<162::aid-anie162>3.0.co;2-u

Cited by 51 publications

(54 citation statements)

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“…24 These results afforded novel products and also provided clues to the identity of the 'red compound' always formed during the preparation of 5. Stirring equimolar mixtures of [8,8- (14). NMR spectra, elemental analysis, and high-resolution mass spectrometry were consistent with the formulation, which was confirmed by a single crystal X-ray diffraction study ( Fig.…”

Section: Formation Of An Isonido-rhodathiaboranesupporting

confidence: 60%

Organometallic chemistry on rhodaheteroborane clusters: reactions with bidentate phosphines and organotransition metal reagents

Volkov

Macı́as

Rath

et al. 2003

Applied Organom Chemis

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This article reviews our recent work on the reactions of the rhodaheteroboranes [8,8-(PPh 3 ) 2 -nido-8,7-RhSB 9 H 10 ] (1) and [9,9-(PPh 3 ) 2 -nido-9,7,8-RhC 2 B 8 H 11 ] (2), and their derivatives, with the bidentate phosphines, dppe [(CH 2 ) 2 (PPh 2 ) 2 ], dppp [(CH 2 ) 3 (PPh 2 ) 2 ], and dppm [CH 2 (PPh 2 ) 2 ], and also with organotransition metal reagents. Simple substitution of the two PPh 3 ligands by a single bidentate phosphine takes place when a 1 : 1 molar ratio of base (dppe or dppp) to rhodathiaborane (1) is used. However, in the presence of an excess of dppe or dppp, products containing 1 or 2 mol of base are formed. These products include a bidentate ligand on the metal and a monodentate ligand on the cage. The displaced hydrogen atom from the cage has moved to the metal center. These bis(ligand) species are unstable with respect to the loss of dihydrogen, affording closo-11 vertex clusters with a pendent phosphine ligand on the cage. In concentrated solutions, the pendent phosphine attacks another cage to afford linked clusters. Under both sets of conditions, when dppm is used, only one product is observed. This species has two dppm ligands coordinated to the metal: one in a unidentate mode and the other bidentate. A similar product is obtained in the reaction of 2 with dppm, although the arrangement of the ligands on the metal in the product is different. Ligand exchange experiments on the dppm-thiaborane system lead to results that provide keys to the reaction pathways in some of these processes. The bis(dppm) derivatives of 1 and 2 are amenable to further derivatization. A second metal may be added, either as an exo-polyhedral atom in a nido cluster in which the metal is part of a bidentate ligand, in the case of 1 and 2, or in a closo cluster derivative of 1 in which the metal is bonded to a dangling PPh 2 moiety. Thus, it was possible to add the metals iridium, rhodium or ruthenium to the cluster, in the case of 1 and ruthenium in the case of 2. However, the reaction of more electrophilic organotransition metal reagents, such as Wilkinson's catalyst, with the dppm derivative of 1 affords species resulting from removal of ligand rather than incorporation of metal, and the products shed light on the rearrangement processes in these systems.

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Section: Formation Of An Isonido-rhodathiaboranesupporting

confidence: 60%

Organometallic chemistry on rhodaheteroborane clusters: reactions with bidentate phosphines and organotransition metal reagents

Volkov

Macı́as

Rath

et al. 2003

Applied Organom Chemis

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“…Since the report of the first nonclassical dihydrogen complex [2] in 1984, numerous examples of agostic bond of dihydrogen [3][4][5][6][7][8][9][10][11] and silane [12][13][14][15][16][17][18][19][20] complexes have been reported. In contrast to the large number of dihydrogen complexes and r-silane complexes, reports on stable r-complexes of three coordinated boranes are scarce [21][22][23][24][25][26][27][28][29]. Borane r complexes of titanium, manganese and rhenium reported by Hartwig et al are the most representative examples with coordination of the B-H bond of a neutral borane to a transition metal center [21][22][23][24].…”

Section: Introductionmentioning

confidence: 99%

Structure and coordinate bonding nature of the manganese–σ–borane complexes

Pandey

2007

Journal of Organometallic Chemistry

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“…Thus, the chelating phosphine borane H 3 B AE PPh 2 -CH 2 PPh 2 (H 3 B AE dppm) [7] (structure B Scheme 1) forms stable complexes that do not suffer from spontaneous decomposition or facile displacement of the MÁ Á Á HB interaction. Nido-Rh(g 2 -H 3 B AE dppm)(SB 9 H 10 ) [8] Cr(CO) 4 (g 1 -H 3 B AE dppm) [9], [Rh(cod)(g 2 -H 3 B AE dppm)]-[PF 6 ] [10] are examples of such complexes. 1 Coordination compounds of the chelating diborane ligand B 2 H 4 AE (PMe 3 ) 2 (C) have also been reported, and this ligand can either adopt a monodentate or a bidentate binding mode such as Cr(CO) 5 in that the borane ligand can change from g 2 to g 1 , effectively providing a reactive 16-electron {RuCp* (g 1 -H 3 B AE dppm)} + fragment.…”

Section: Introductionmentioning

confidence: 99%