Synthesis and characterization of the novel gold-iridium cluster [IrAu4(H)2(PPh3)6]BF4

Casalnuovo, A. L.; Casalnuovo, J. A.; Nilsson, P. V.; Pignolet, L. H.

doi:10.1021/ic00210a018

Cited by 26 publications

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“…The Ru-H distance is slightly longer than values previously observed for hydrides bridging Áu-Ru bonds (1.61 (4) A in the Au2Ru(dppm)2 complex,51.71 (6) A in the AuRu(dppm)2 complex,2 typical range 1.6-1.9 A66,67). The Au-H distance is slightly shorter than previously determined values [1.77 (4) A in the Au2Ru(dppm)2 complex,5 1.98 (6) A in the AuRu(dppm)2 complex,2 1.7 (1) A in AuCr(M-H)(CO)5(PPh3),64 and 1.72 (9) A in [AuPt(M-H)(C6F5)(PEt3)2(PPh3)](CF3S03)18], but these differences are barely significant. The Au-Ru distance (2.786 (1) A) is similar to that found in the Au2Ru(dppm)2 complex (average 2.781 (0) A)5 but longer than that in the AuRu(dppm)2 complex (2.694 (I) A).2 This result is surprising, since 3 and the AuRu(dppm)2 complex have the same sort of Au-Ru bond bridged by two hydride ligands; however, the shorter Au-Ru bond in the AuRu(dppm)2 complex may be due to the less steric dppm ligands.…”

Section: Resultscontrasting

confidence: 57%

Heterobimetallic gold-osmium and gold-ruthenium hydrido complexes. X-ray crystal and molecular structures of [Au2Os(H)3(PPh3)5]PF6 and [AuRu(H)2(CO)(PPh3)4]PF6

Alexander¹,

Gomez-Sal²,

Gannon³

et al. 1988

Inorg. Chem.

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Several new heterobimetallic hydrides containing gold have been synthesized. [Au2Os(H)3(PPh3)5]PF6 (1) was made by the reaction of AuPPh3NQ3 and Os(H)4(PPh3)3 with CH2C12 as solvent. [Au2Ru(H)3(PPh3)5]PF6 (2) was synthesized in an analogous manner from AuPPh3NQ3 and Ru(H)4(PPh3)3 with toluene as solvent. [AuRu(H)2(CO)(PPh3)4]PF6 (3) and its osmium analogue, [AuOs(H)2(CO)(PPh3)4]PF6 (4), and [AuOs(H)2(CO)2(PPh3)3]PF6 (5) and its ruthenium analogue, [AuRu(H)2(CO)2(PPh3)3]PF6 (6), were prepared by the reaction of AuPPh3N03 with M(H)2(CO)(PPh3)3 (M = Ru, Os) and M(H)2(CO)2(PPh3)2 ( = Ru, Os), respectively, with CH2C12 as solvent. Compounds 1 and 3 were characterized by single-crystal X-ray diffraction in the solid state [l-3CH2Cl2.2Et20, monoclinic P2¡/n, a = 13.64 (2) A, b = 40.89 (2) k,c= 17.53 (1) A, ß = 102.54 (9)°, = -116 °C, Z = 4,R = 0.051 for 10 180 observations; 3-2CH2Cl2, triclinic PI, a = 15.404 (3) A, b = 19.461 (8) A, c = 13.868 (7) k, a = 98.86 (4)°, ß -105.68 (3)°, y = 87.73 (2)°, T = 22 °C, Z = 2, R = 0.051 for 9648 observations] and by 31P and NMR spectroscopy in solution. The structure of complex 1 consists of two Au(PPh3) units bonded to an Os(PPh3)3 moiety forming a slightly distorted trigonal-bipyramidal geometry with no Au-Au bond (4.28 A). The hydride ligands were not directly observed by X-ray diffraction in 1; however, spectroscopic evidence indicates the presence of one hydride bridging each of the Au-Os bonds on the outside edges of the Au2Os triangle and a third hydride briding one of the Au-Os bonds on the inside edge of the Au2Os triangle. Supporting evidence for the characterization of complex 1 in the solid state was obtained with the use of CP MAS 31P NMR spectroscopy. In the X-ray diffraction analysis of complex 3 one of the hydride ligands was directly observed bridging the Au-Ru bond. Spectroscopic evidence supports the formulation of 3 as a bis(g-hydrido) species. The average Au-Os and Au-Ru distances in 1 and 3 are 2.703 (0) and 2.786 (1) A, respectively, and the Ru-H and Au-H separations in 3 are 1.78 (4) and 1.61 (4) A, respectively. Compounds 2 and 4-6 were also determined to have bridging hydrides by NMR and IR spectroscopy. Preliminary results indicate that the gold adduct [AuRu(H)2(CO)(PPh3)4]PF6 (3) has a significantly higher rate of catalytic activity than its parent complex, Ru(H)2(CO)(PPh3)3, for the isomerization of 1-hexene to cis-and trans-2-hexene in CH2C12 at 25 °C and 1 atm of N2.

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Section: Resultscontrasting

confidence: 57%

Heterobimetallic gold-osmium and gold-ruthenium hydrido complexes. X-ray crystal and molecular structures of [Au2Os(H)3(PPh3)5]PF6 and [AuRu(H)2(CO)(PPh3)4]PF6

Alexander¹,

Gomez-Sal²,

Gannon³

et al. 1988

Inorg. Chem.

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“…In complex 6 though, the Au(I) ion sits directly over the Ir(I) ion suggesting a Ir-Au interaction. However, it is clear no bond exists since the atoms are separated by 3.2770(3) Å, a distance that is well-outside the range reported for Ir-Au bonds of 2.59 Å-2.81 Å [53][54][55][56][57][58][59][60][61][62].…”

Section: 6supporting

confidence: 58%

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“…The molecular structure of compound 1 is similar to that of the previously characterized iridium-gold complex, [Au4Ir(H)2(PPh3)6]BF4 (5). 14 Both consist of an approximately trigonal-bipyramidal (TBP) core with one hydride bridging each of the axial M-Au bonds, as (28) Douglas, G.; Jennings, M. C.; Manojlovic-Muir, L.; Puddephatt, J.…”

Section: Introductionmentioning

confidence: 56%

“…12,18 Typically, we find that the bridging M^-//)AuPPh3 coupling constants are greater than 20 Hz and terminal 7/M-AuPPh3 coupling constants are less than 15 Hz. 1,12,14 The value of 17.7 Hz, however, is an average of all four PAu-H coupling constants due to the rapid rearrangement of 1 in solution. Therefore, it is likely that the two hydrides occupy bridiging positions and that 7Pau_h for the bridging interaction is larger than 17.7 Hz.…”

Section: Methodsmentioning

confidence: 99%

Synthesis and characterization of cationic gold-rhodium phosphite cluster complexes. X-ray crystal and molecular structure of {Au4Rh(H)2[P(O-iso-C3H7)3]2(PPh3)4}PF6

Alexander¹,

Mueting²,

Pignolet³

1990

Inorg. Chem.

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= 3) have been investigated. |Au4Rh(H)2[P(0-i-C3H7 )3]2(PPh3)4jPF6 (1) and |Au5Rh(H)[P(OCH3)3]2(PPh3)5|PF6 (2) were synthesized by the reaction of Au(PPh3)N03 and |Rh(H)[P(0-z-C3H7)3]2]2 or |Rh(H)[P(OCH3)3]2)3, respectively, with THF as solvent. |Au6Rh(H)[P-(OCH3)3]2(PPh3)6|(PF6)2 (3) was made by further reaction of Au(PPh3)N03 and 2 with CH2C12 as solvent. Compound 1 was characterized by single-crystal X-ray diffraction in the solid state [1, Pi (No. 2), a = 14.38 (1) Á, 6 = 14.50 (2) A, c = 26.81 (2) A, a = 101.98 (10)°, ß = 89.03 (7)°, y = 117.82 (10)°, T = -95 °C, Z = 2, R = 0.042 for 8,142 observations] and by 31P and NMR spectroscopy in solution. The molecular structure of complex 1 consists of an approximately trigonal-bipyramidal (TBP) RhAu4 core with a Rh[P(0-/-C3H7)3]2 unit occupying an equatorial position. The four AuPPh3 units occupy the axial positions and the two remaining equatorial positions. The major deviation from ideal TBP geometry is reflected in the shorter Au-Rh distances (average 2.685 (1) A) compared with the bonded Au-Au separations (average 2.904 (1) A). The hydride ligands were not directly observed by X-ray diffraction in 1; however, spectroscopic evidence, potential energy calculations, and the solid-state structural results (average distances: axial Au-Rh = 2.717 (1) A; equatorial Au-Rh = 2.654 (1) A) indicate the presence of one hydride bridging each of the longer Au-Rh bonds. Compounds 2 and 3 were characterized by IR and *H and 31P NMR spectroscopies. Compounds 2 and 3 were each determined to possess one bridging hydride ligand.

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Synthesis and characterization of the novel gold-iridium cluster [IrAu4(H)2(PPh3)6]BF4

Cited by 26 publications

References 4 publications

Heterobimetallic gold-osmium and gold-ruthenium hydrido complexes. X-ray crystal and molecular structures of [Au2Os(H)3(PPh3)5]PF6 and [AuRu(H)2(CO)(PPh3)4]PF6

Heterobimetallic gold-osmium and gold-ruthenium hydrido complexes. X-ray crystal and molecular structures of [Au2Os(H)3(PPh3)5]PF6 and [AuRu(H)2(CO)(PPh3)4]PF6

Expanding iClick to group 9 metals

Synthesis and characterization of cationic gold-rhodium phosphite cluster complexes. X-ray crystal and molecular structure of {Au4Rh(H)2[P(O-iso-C3H7)3]2(PPh3)4}PF6

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