Protonation reactions of the mononuclear rhenium polyhydride complexes [ReH7(PPh3)2], [ReH5(PPh3)2L](L = unidentate ligand), and [ReH4I(PPh3)3]

Allison, Joe D.; Moehring, Gregory A.; Walton, Richard A.

doi:10.1039/dt9860000067

Cited by 11 publications

(20 citation statements)

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“…δ −2 and −10. This spectrum differs from the ambient-temperature hydride-region 1 H NMR spectrum of a monophosphine analogue of 8 , ReH 4 I(PPh 3 ) 3 , which shows a quartet of relative intensity 4. When a solution of 8 is cooled to 240 K, three sharp resonances are obtained: two triplets, at δ −2.23 ( 2 J PH = 27.9 Hz) and −4.34 ( 2 J PH = 27.5 Hz), and a multiplet at δ −10.48 with relative intensities 1:2:1, respectively.…”

Section: Resultsmentioning

confidence: 57%

Rhenium Polyhydride Complexes Containing PhP(CH₂CH₂CH₂PCy₂)₂(Cyttp): Protonation, Insertion, and Ligand Substitution Reactions of ReH₅(Cyttp) and Structural Characterization of ReH₅(Cyttp) and [ReH₄(η²-H₂)(Cyttp)]SbF₆

et al. 1996

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Several new polyhydride complexes of rhenium containing the tridentate phosphine PhP(CH(2)CH(2)CH(2)PCy(2))(2) (Cyttp) were synthesized and characterized by (1)H and (31)P{(1)H} NMR and IR spectroscopy. The solid state structure of the previously reported ReH(5)(Cyttp) (1) was determined by X-ray crystallography. 1 crystallizes in the space group P2(1)/m with the following unit cell parameters: a = 8.582(2) Å, b = 19.690(2) Å, c = 10.800(2) Å, beta = 95.57(1) degrees, and Z = 2. The molecule adopts a classical polyhydride, triangulated dodecahedral structure, with the three phosphorus atoms and one hydrogen atom occupying the B sites, and the remaining hydrogen atoms occupying the A sites. 1 is protonated by HSbF(6) (or HBF(4)) to yield [ReH(4)(eta(2)-H(2))(Cyttp)]SbF(6) (3), which was shown by X-ray diffraction techniques (space group P&onemacr;, unit cell parameters: a = 9.874(2) Å, b = 14.242(4) Å, c = 16.198(2) Å, alpha = 99.12(2) degrees, beta = 98.85(2) degrees, gamma = 109.42(2) degrees, and Z = 2) to contain a nonclassical polyhydride cation with a triangulated dodecahedral structure in the solid. The same structure is suggested in solution by (1)H NMR data (including T(1) measurements). 3 is inert to loss of H(2) and is unaffected by CO, t-BuNC, and P(OMe)(3) at room temperature. In contrast, 1 reacts with a variety of reagents to afford classical tetrahydride complexes which are thought also to possess a triangulated dodecahedral structure, with the hydrogens in the A sites, from spectroscopic evidence. Accordingly, CS(2), p-O(2)NC(6)H(4)NCS, and EtOC(O)NCS (X=C=S) insert into an Re-H bond to yield ReH(4)(SCH=X)(Cyttp) (5-7, respectively). MeI cleaves one Re-H bond to afford ReH(4)I(Cyttp) (8), and [C(7)H(7)]BF(4) abstracts hydride in the presence of MeCN, t-BuNC, CyNC, or P(OMe)(3) (L) to give [ReH(4)L(Cyttp)]BF(4) (9-12, respectively). A related pentahydride, ReH(5)(ttp) (2, ttp = PhP(CH(2)CH(2)CH(2)PPh(2))(2)), also reacts with HSbF(6) to yield [ReH(6)(ttp)]SbF(6) (4), which appears to be a nonclassical polyhydride in solution by T(1) measurements.

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Section: Resultsmentioning

confidence: 57%

Rhenium Polyhydride Complexes Containing PhP(CH₂CH₂CH₂PCy₂)₂(Cyttp): Protonation, Insertion, and Ligand Substitution Reactions of ReH₅(Cyttp) and Structural Characterization of ReH₅(Cyttp) and [ReH₄(η²-H₂)(Cyttp)]SbF₆

et al. 1996

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“…A synthesis for [ 4 ] + had already been reported in the literature by Walton et al in 1986. Deprotonation and phosphine exchange of the Re III hydride species [ReH(NCCH 3 ) 4 (PPh 3 ) 2 ](BF 4 ) 2 with dppe gave [ 4 ]BF 4 . X-ray diffraction analysis of the so far unreported structure of the cation [ 4 ] + (Figure ) displays similar structural features as found with the nitrile containing cation in the complex double salt [ trans -Re(dppe) 2 (NCC 6 H 4 Me-4) 2 ][ trans -Re(dppe) 2 F 2 ](BF 4 ) 2 .…”

Section: Resultsmentioning

confidence: 99%

Fully Solvated, Monomeric Re^II Complexes: Insights into the Chemistry of [Re(NCCH₃)₆]²⁺

et al. 2020

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The oxidation of [Re( 6 -C10H8)2] + with Ag I in acetonitrile yields [Re(NCCH3)6] 2+ . This fully solvated Re II compound was characterized by spectroscopic methods and X-ray structure analyses. We show that [Re(NCCH3)6] 2+ acts as a precursor complex for a variety of substitution reactions. Treatment with monodentate triphenyl phosphine (PPh3) and bidentate 1,2bis(diphenylphosphino)ethane (dppe) yields the Re I complexes [trans-Re(PPh3)2(NCCH3)4] 2+ and [trans-Re(dppe)2(NCCH3)2] + , respectively. [trans-Re(dppe)2(NCCH3)2] + is oxidized under mild conditions by Ag I to its Re II analogue [trans-Re(dppe)2(NCCH3)2] 2+ . Reactions of [Re(NCCH3)6] 2+ with a halide mixture consisting of NaX and AgX (X = Cl, I) results in the formation of the corresponding Re III complexes [trans-ReX2(NCCH3)4] + . [trans-ReBr2(NCCH3)4] + can be obtained directly from [Re( 6 -C10H8)2] + by oxidation with FeBr3 in acetonitrile. The title compound is thus a convenient starting material for Re II and Re III complexes by simple solvent exchange, which are otherwise difficult to access.

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“…We began our investigation of the bound imine functional group by treating the ReH 4 [η 2 -(1,2-C 6 H 4 )CHNR](PPh 3 ) 2 compounds with tetrafluoroboric acid−diethyl ether complex (HBF 4 ·Et 2 O), in acetonitrile. The rhenium-containing product from the acidolysis of each ReH 4 [η 2 -(1,2-C 6 H 4 )CHNR](PPh 3 ) 2 compound was found to be [ReH(NCMe) 4 (PPh 3 ) 2 ](BF 4 ) 2 . The effervescence of a gaseous product was also found during the acidolysis reaction of each ReH 4 [η 2 -(1,2-C 6 H 4 )CHNR](PPh 3 ) 2 compound.…”

Section: Resultsmentioning

confidence: 93%

“…Starting Materials. The complexes ReH 7 (PPh 3 ) 2 , Re 2 H 8 (PPh 3 ) 4 and [ReH(NCMe) 4 (PPh 3 ) 2 ](BF 4 ) 2 were prepared by standard literature methods. ,, All other reagents and solvents were obtained from commercial sources. All reactions were performed under an atmosphere of nitrogen.…”

Section: Methodsmentioning

confidence: 99%

“…There has been considerable interest in the reactions of ReH 7 (PPh 3 ) 2 with nitrogen donor molecules. − The reactions of ReH 7 (PPh 3 ) 2 with simple imines (R 2 CNR), however, have been unexplored. Meanwhile, reactions between simple imines and other transition metal complexes have drawn much attention. − Such reactions have produced complexes which include N-bound imine ligands, bidentate ortho -metalated ligands, iminoacyl ligands, bridging amide ligands, and ligands which result from coupling of the imine functional group with other unsaturated functional groups.…”

Section: Introductionmentioning

confidence: 99%

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Structural Determination and Acidolysis Reactions ofOrtho-Metalated Rhenium Tetrahydride Compounds Prepared from Reactions of ReH₇(PPh₃)₂with Benzylic Imines

et al. 1998

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Reactions between ReH(7)(PPh(3))(2) and a series of benzylic imines, PhCHNR (R = Me, Ph, or Bn), produce the compounds ReH(4)[eta(2)-(1,2-C(6)H(4))CHNR](PPh(3))(2). One such compound, ReH(4)[eta(2)-(1,2-C(6)H(4))CHNPh](PPh(3))(2), was characterized by X-ray diffraction analysis. The compound ReH(4)[eta(2)-(1,2-C(6)H(4))CHNPh](PPh(3))(2) crystallizes in the P(&onemacr;) space group with the following unit cell dimensions: a = 12.422(3) Å, b = 12.696(3) Å, c = 13.604(5) Å, alpha = 93.26(2) degrees, beta = 90.66(2) degrees, gamma = 107.03(2) degrees, V = 2047.2 Å(3), and Z = 2. The structure was refined to R(F(o)) = 0.029 (R(w)(F(o)) = 0.034) for 5352 data with I > 3.0sigma(I). The structure determination indicates that ortho-metalation of the imine reactant occurs during the reaction of ReH(7)(PPh(3))(2) with PhCHNPh. The observation of four nu(Re-H) absorptions in the infrared spectrum of each ReH(4)[eta(2)-(1,2-C(6)H(4))CHNR](PPh(3))(2) compound indicates that the rhenium-bound hydrogen atoms, in these compounds, are better regarded as classical hydride ligands rather than as elongated dihydrogen ligands. Acidolysis reactions of the compounds ReH(4)[eta(2)-(1,2-C(6)H(4))CHNR](PPh(3))(2), with HBF(4).Et(2)O in acetonitrile, result in loss of the ortho-metalated imine ligands from the rhenium coordination spheres and in reduction of the imine functional groups to secondary ammonium cations. One hydride ligand is transferred to the imine carbon atom, during the course of each acidolysis reaction.

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Protonation reactions of the mononuclear rhenium polyhydride complexes [ReH7(PPh3)2], [ReH5(PPh3)2L](L = unidentate ligand), and [ReH4I(PPh3)3]

Cited by 11 publications

References 2 publications

Rhenium Polyhydride Complexes Containing PhP(CH₂CH₂CH₂PCy₂)₂(Cyttp): Protonation, Insertion, and Ligand Substitution Reactions of ReH₅(Cyttp) and Structural Characterization of ReH₅(Cyttp) and [ReH₄(η²-H₂)(Cyttp)]SbF₆

Rhenium Polyhydride Complexes Containing PhP(CH₂CH₂CH₂PCy₂)₂(Cyttp): Protonation, Insertion, and Ligand Substitution Reactions of ReH₅(Cyttp) and Structural Characterization of ReH₅(Cyttp) and [ReH₄(η²-H₂)(Cyttp)]SbF₆

Fully Solvated, Monomeric Re^II Complexes: Insights into the Chemistry of [Re(NCCH₃)₆]²⁺

Structural Determination and Acidolysis Reactions ofOrtho-Metalated Rhenium Tetrahydride Compounds Prepared from Reactions of ReH₇(PPh₃)₂with Benzylic Imines

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Protonation reactions of the mononuclear rhenium polyhydride complexes [ReH7(PPh3)2], [ReH5(PPh3)2L](L = unidentate ligand), and [ReH4I(PPh3)3]

Cited by 11 publications

References 2 publications

Rhenium Polyhydride Complexes Containing PhP(CH2CH2CH2PCy2)2(Cyttp): Protonation, Insertion, and Ligand Substitution Reactions of ReH5(Cyttp) and Structural Characterization of ReH5(Cyttp) and [ReH4(η2-H2)(Cyttp)]SbF6

Rhenium Polyhydride Complexes Containing PhP(CH2CH2CH2PCy2)2(Cyttp): Protonation, Insertion, and Ligand Substitution Reactions of ReH5(Cyttp) and Structural Characterization of ReH5(Cyttp) and [ReH4(η2-H2)(Cyttp)]SbF6

Fully Solvated, Monomeric ReII Complexes: Insights into the Chemistry of [Re(NCCH3)6]2+

Structural Determination and Acidolysis Reactions ofOrtho-Metalated Rhenium Tetrahydride Compounds Prepared from Reactions of ReH7(PPh3)2with Benzylic Imines

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Rhenium Polyhydride Complexes Containing PhP(CH₂CH₂CH₂PCy₂)₂(Cyttp): Protonation, Insertion, and Ligand Substitution Reactions of ReH₅(Cyttp) and Structural Characterization of ReH₅(Cyttp) and [ReH₄(η²-H₂)(Cyttp)]SbF₆

Rhenium Polyhydride Complexes Containing PhP(CH₂CH₂CH₂PCy₂)₂(Cyttp): Protonation, Insertion, and Ligand Substitution Reactions of ReH₅(Cyttp) and Structural Characterization of ReH₅(Cyttp) and [ReH₄(η²-H₂)(Cyttp)]SbF₆

Fully Solvated, Monomeric Re^II Complexes: Insights into the Chemistry of [Re(NCCH₃)₆]²⁺

Structural Determination and Acidolysis Reactions ofOrtho-Metalated Rhenium Tetrahydride Compounds Prepared from Reactions of ReH₇(PPh₃)₂with Benzylic Imines