Rhodium(I) and rhodium(III) phosphine complexes with nonbridging benzenethiolato ligands: preparation, structures, and chemical properties

Osakada, Kohtaro; Hataya, Kouji; Yamamoto, Takakazu

doi:10.1021/ic00063a027

Cited by 42 publications

(17 citation statements)

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“…Similar behavior was also observed in complex 4. In that case, the 19 F chemical shifts of the fluorine atom which is located ortho to the P V were shifted by 16 ppm to low field suggesting that one of the phenyl substituents on P V lies physically close to this fluorine. The CO stretching frequency of 5 is 1979 cm -1 , consistent with a cis phosphine-carbonyl structure.…”

Section: Table 4 Selected Bond Distances (å) Inmentioning

confidence: 94%

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New Heteromultifunctional Fluoroaromatic Bis(phosphinimine) Ligands and Their Complexes. Synthesis and Characterization of New Ligands (Including X-ray Structures of 4,6-(CN)₂C₆F₂-1-(NP(Ph)₂CH₂PPh₂)-3-(NPPh₃) and 4,6-(CN)₂C₆F₂-1,3-bis(NP(Ph)₂CH₂PPh₂)) and Their Rhodium(I) Complexes, Including the Structure of the Novel Dimetallic Complex 4,6-(CN)₂C_6<

McDonald

Cavell

1996

Organometallics

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Reaction of 1,3-dicyanotetrafluorobenzene with trimethylsilyl phosphinimines proceeds through stepwise substitution on the fluoroaromatic to yield mono-and ultimately disubstituted derivatives of the form 4,6-(CN) 2 C 6 F 2 -1-A-3-B. Two molar equivalents of a bifunctional phosphinophosphoranimines, Me 3 SiNP(Ph) 2 CH 2 PPh 2 , result in a dual substitution giving 1 (A ) B ) (NdP(Ph) 2 CH 2 PPh 2 )), whereas 1 equiv of the trimethylsilyl phosphinimine gives the monosubstituted derivative. Treatment of the monosubstituted derivative with a second 1 equiv of the same or a different phosphinimine gives doubly substituted derivatives which can have the same or different phosphorus substituents, e.g. and 2, 4,6-), have been structurally characterized. In 1, the P(1)dN(1) bond length is 1.581(3) Å, the P(3)dN(2) bond length is 1.569(4) Å, the P(1)-N(1)-C(6) angle is 132.1(3)°, and the P(3)-N(2)-C(2) angle is 133.2(3)°. For 2, the P(2)dN(1) bond length (in the Ph 3 PdN unit) is 1.578(4) Å, the P(3)dN(2) bond length in the Ph 2 PCH 2 Ph 2 PdN unit) is 1.585(4) Å, the P(2)-N(1)-C(2) angle is 134.7(4)°, and the P(3)-N(2)-C(6) angle is 129.9-(4)°. 2 reacted readily with [Rh(CO) 2 Cl] 2 to form the mono metallic chelated Rh complex 4, 4,6-(CN) 2 C 6 F 2 -3-(NdPPh 3 )-1-(NdP(Ph) 2 CH 2 P(Ph) 2 Rh(CO)Cl). 1 reacts with both 1 equiv and 0.5 equiv of [Rh(CO) 2 Cl] 2 to form respectively 4,6-(CN) 2 C 6 F 2 -1,3-bis(NdP(Ph) 2 CH 2 P(Ph) 2 Rh-(CO)Cl), 5, and 4,6-(CN) 2 C 6 F 2 -1,3-bis(NdP(Ph) 2 CH 2 P(Ph) 2 )Rh(CO)Cl, 6. The half-metalated complex 6 can be converted to 5 with a second aliquot of the Rh precursor, and the dimetalated complex 5 can be converted to the half-metalated complex 6 by reaction of 5 with more ligand. The bis(phosphine) chelate structure of 6, the dimetalated complex, was deduced from the complex second-order 31 P NMR spectrum solved by simulation. The two P III are trans coordinated to the Rh center, and the two N are not coordinated. There is no P III -P III or P V -P V coupling, but each P III is coupled to two magnetically inequivalent P V . Structural characterization of the dimetalated complex 5 shows a symmetrically substituted complex containing two Rh centers with a square planar geometry around each Rh(I) with the CO cis to the phosphine. Bond angles and lengths are typical for the Rh(I) square planar chelate complex structures. The P(1)-N(1) distance of 1.61(1) Å in the complex is normal for a coordinated iminophosphoranyl group. The directly bound Rh-P III distance of 2.206-(4) Å also lies within the range found in many Rh(I) phosphine complexes of this type.

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Section: Table 4 Selected Bond Distances (å) Inmentioning

confidence: 94%

“…2 The directly bound Rh-P III distance of 2.206(4) Å also lies within the range found in many Rh(I) phosphine complexes of the type P 2 Rh(CO)Cl. [13][14][15][16][17][18][19] (13) Bennett, M. J.; Donaldson, P. B. J. Am.…”

Section: Table 4 Selected Bond Distances (å) Inmentioning

confidence: 99%

New Heteromultifunctional Fluoroaromatic Bis(phosphinimine) Ligands and Their Complexes. Synthesis and Characterization of New Ligands (Including X-ray Structures of 4,6-(CN)₂C₆F₂-1-(NP(Ph)₂CH₂PPh₂)-3-(NPPh₃) and 4,6-(CN)₂C₆F₂-1,3-bis(NP(Ph)₂CH₂PPh₂)) and Their Rhodium(I) Complexes, Including the Structure of the Novel Dimetallic Complex 4,6-(CN)₂C_6<

McDonald

Cavell

1996

Organometallics

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“…The same contraction in Rh-P bonds trans to the "X" ligand are found in Rh(PMe 3 ) 3 Cl, Rh(PMe 3 ) 3 (S-C 6 H 5 ), and Rh(PMe 3 ) 3 (OpTol) where the Rh-P distance is shorter than the mutually trans Rh-PMe 3 distance by 0.095(1) Å, 0.063(3) Å, and 0.1058(11) Å respectively. [24][25][26] This observation is likely due to the π-basic nature of these anionic ligands resulting in extra electron density available at the metal to overlap in a π fashion with PMe 3 . In contrast the mutually trans PMe 3 ligands compete with each other to accept electron density for π-bonding.…”

Section: Table 2 Selected Bond Lengths (å) and Angles (°) Formentioning

confidence: 99%

Rhodium pyrazolate complexes as potential CVD precursors

et al. 2012

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5). Two of the complexes, 1 and 3, were studied for use as CVD precursors. Polycrystalline thin films of rhodium (fccRh) and metastable-amorphous films of rhodium phosphide (Rh 2 P) were grown from 1 and 3 respectively at 170 and 130°C, 0.3 mmHg in a hot wall reactor using Ar as the carrier gas (5 cc min −1 ). Thin films of amorphous rhodium and rhodium phosphide (Rh 2 P) were grown from 1 and 3 at 170 and 130°C respectively at 0.3 mmHg in a hot wall reactor using H 2 as the carrier gas (7 cc min −1 ).

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“…Q Crystal data for 2a: Cz7W3RhSSi, M, = 624.63, triclinic, space group P i (no. 2), a = 10.856 (5), h = 14.134 (6), c = 10.842(5) A, a = 97.07(4), f~ = 106.64 (5), y = 80.10( 4)", U = 1055 w 3 , Z = 2, D, = 1.325 g cm-3, p = 8.030 cm-l, F(000) = 652, graphite-monochromated Mo-Ka radiation (h = 0.71069 A). The structure was solved by direct methods and refined by full-matrix least-squares techniques to R = 0.022, R , = 0.035 using 65 19 reflections with F , 2 3o(F,).…”

Section: Footnotesmentioning

confidence: 99%

“…1 A perspective drawing of complex 2a. Selected bond lengths (A) and angles ("): Rh-P( 1) 2.326( l), Rh-P(2) 2.336(1), Rh-P(3) 2.331( l), Rh-Si 2.342( l), Rh-H( 1) 1.57(2), Rh-H(2) 1.63(2), Si-S 2.228( I), S i x ( 10) 1.907(2), S i x ( 1 6) 1.9 1 3( 2), P( I)-Rh-P(2) 1 00.00 (5), P( 1 )-Rh-P( 3) 96.24 (5), P( 1)-Rh-Si 100.74 (5), P( 1)-Rh-H( 1) 173.6(8), P( 1)-Rh-H(2) 89.2( 8) , P(2)-Rh-P( 3) 1 00.95 (5), P( 2 We are grateful to Dr Masako Tanaka for her help in the crystallographic study. This work was financially supported by Grants-in-Aid for Scientific Research from the Ministry of Education, Science and Culture, Japan, and by Asahi Glass Foundation.…”

mentioning

confidence: 99%