Synthesis and substitution reactions of tris- and tetrakis(trimethyl phosphite)-substituted carbyne complexes of chromium, molybdenum, and tungsten

Mayr, Andreas; Dorries, Alison M.; McDermott, Gregory A.; Engen, D. Van

doi:10.1021/om00138a037

Cited by 26 publications

(12 citation statements)

References 0 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The short MoÀC bond length of 1.773(2) confirms the triple-bond character being similar to the reported Mo IV alkylidyne species, [19] although the Mo1-C1-C2 angle shows some deviation from linearity (163.97 (19)8), presumably for steric reasons. The 11 B and 19 F NMR spectra of 2 both show quaternization at boron: the boron atom appears as a singlet at d = À15.4 ppm, while the 19 F NMR spectrum shows the expected signals at d = À130.4, À162.5, and À165.4 ppm for the C 6 F 5 groups.…”

supporting

confidence: 82%

See 1 more Smart Citation

Alkene to Carbyne: Tandem Lewis Acid Activation and Dehydrogenation of a Molybdenum Ethylene Complex

2013

View full text Add to dashboard Cite

show abstract

supporting

confidence: 82%

supporting

confidence: 72%

Alkene to Carbyne: Tandem Lewis Acid Activation and Dehydrogenation of a Molybdenum Ethylene Complex

2013

View full text Add to dashboard Cite

show abstract

“…1829(1) 1 829(2) 2 633(2) 3 063 ( 10) 4 161 (11) 5 074 ( 11) 6 049 ( 12) 6 176 (11) 7 251 (12) 5 289 ( 12) 4 304( 14) 817(13) 1 410( 15) 241(13) 3 I3( 15) 1056(13) 1(13) 520 ( 12) -232( 13) -2(4) 1435(4) 1553( 8) 1962( 7) 1843 (6) 2 031( 7) 1036 (7) 822(9) 1 309 (5) 876( 6) Z = 8, F(000) = 3 343.5, space group P2,/c, Mo-K, Xradiation (graphite monochromator), x = 0.710 69 A, p(Mo-K,) = 18.19 cm-'.…”

Section: 'mentioning

confidence: 99%

Chemistry of polynuclear metal complexes with bridging carbene or carbyne ligands. Part 86. Aikylidyne(carbaborane)molybdenum–gold, –rhodium and –iron complexes; crystal structure of [NEt₄][MoFe₂(µ₃-CC₆H₄Me-4)(µ-σ : σ′ : η⁵C₂B₉H₇Me₂)(CO)₈]

Devore¹,

Emmerich²,

Howard³

et al. 1989

J. Chem. Soc., Dalton Trans.

View full text Add to dashboard Cite

Chemical shifts (6) in p.p.m., coupling constants in Hz. Measurements at ambient temperatures. Measured in CD,Cl,. Proton resonances for the BH groups occur as broad unresolved signals in the range 6 0-3. Hydrogen-1 decoupled, chemical shifts are positive to high frequency of SiMe,, with measurements in CD,CI,-CH,C1,. Peaks for minor isomer, other signals obscured by signals for major isomers. Signal for POMe group obscured by solvent peak. Peaks for major isomer. is likely to be present in (8a) also, since the p-C resonances in the 'C-{ ' H} n.m.r. spectra of the two complexes are so similar and are close to that observed (6 293.8 p.p.m.) for the terminal M o X group in (7). In dimetal complexes with bridging alkylidyne groups the signals for the p-C nuclei are generally significantly more deshielded than 300 ~. p . m . ~~. ~ Compound (8a) appears to be more stable than (8b). In the synthesis of the latter a by-product was the salt [N(PPh,),]-[W2Au(p-CC6H4Me-4)2(CO)4(q5-C2B9H9Me2)2], formed by displacement of the PPh, group in (8b) by the CrW moiety of (lc). No similar trimetal species was observed to form in the reaction between [AuCI(PPh,)] and (7). The reaction between (7) and [Rh(cod)(PPh,>,][PF,] in CH2C1, afforded the compound [MoRh(p-CC6H4Me-4)(p-CO){ P(OMe),}(PPh,),(q5-C,B,H,Me2)] (9a), data for which are summarised in Tables 1-3. The related tungsten-rhodium compound [WRh(p-CC6H4Me-4)(p-CO)(CO)(co)(PPh3)2(q5-c2~ B,H,Me,)] (9b) has been prepared by treating the [N(PPh,),] salt of (lc) with [RhCl(PPh,),] or [Rh(cod)(PPh3),][PF6]. An X-ray diffraction study revealed that it contained a strongly

show abstract

“…The synthesis of the 4-iodobenzylidyne and 4-bromobenzylidyne ligands follows established procedures. 5 In the first step, tungsten hexacarbonyl is allowed to react with (4-iodophenyl)lithium and (4-bromophenyl)lithium in diethyl ether to afford the anionic acyl complexes 1 and 2, respectively, which are isolated as the tetramethylammonium salt 9 [equation (1)]. The new alkylidyne tungsten complexes 3-11 exhibit two IR absorptions for the two carbonyl ligands.…”

Section: Resultsmentioning

confidence: 99%

“…The development of metal alkylidyne complexes as functional components in molecular materials requires procedures for the synthesis of extended unsaturated alkylidyne ligands. 4 Currently available methods for the synthesis of alkylidyne metal complexes 2 are efficient as far as the synthesis of the metal-carbon triple bond 5 and the modification of the ancillary ligands are concerned, 6 but provide only limited direct access to functionalized unsaturated alkylidyne ligands, since they involve highly reactive intermediates or reagents which would interfere with the presence of a variety of functional groups. 7 It is therefore necessary to devise procedures which allow the elaboration of unsaturated alkylidyne ligands after formation of the metal-carbon triple bond.…”

mentioning

confidence: 99%

4-Iodobenzylidyne as a precursor ligand for extended unsaturated alkylidyne ligands

Yu¹,

Cheung²,

Mayr³

1998

J. Chem. Soc., Dalton Trans.

Self Cite

View full text Add to dashboard Cite

Synthesis and substitution reactions of tris- and tetrakis(trimethyl phosphite)-substituted carbyne complexes of chromium, molybdenum, and tungsten

Cited by 26 publications

References 0 publications

Alkene to Carbyne: Tandem Lewis Acid Activation and Dehydrogenation of a Molybdenum Ethylene Complex

Alkene to Carbyne: Tandem Lewis Acid Activation and Dehydrogenation of a Molybdenum Ethylene Complex

Chemistry of polynuclear metal complexes with bridging carbene or carbyne ligands. Part 86. Aikylidyne(carbaborane)molybdenum–gold, –rhodium and –iron complexes; crystal structure of [NEt₄][MoFe₂(µ₃-CC₆H₄Me-4)(µ-σ : σ′ : η⁵C₂B₉H₇Me₂)(CO)₈]

4-Iodobenzylidyne as a precursor ligand for extended unsaturated alkylidyne ligands

Contact Info

Product

Resources

About

Synthesis and substitution reactions of tris- and tetrakis(trimethyl phosphite)-substituted carbyne complexes of chromium, molybdenum, and tungsten

Cited by 26 publications

References 0 publications

Alkene to Carbyne: Tandem Lewis Acid Activation and Dehydrogenation of a Molybdenum Ethylene Complex

Alkene to Carbyne: Tandem Lewis Acid Activation and Dehydrogenation of a Molybdenum Ethylene Complex

Chemistry of polynuclear metal complexes with bridging carbene or carbyne ligands. Part 86. Aikylidyne(carbaborane)molybdenum–gold, –rhodium and –iron complexes; crystal structure of [NEt4][MoFe2(µ3-CC6H4Me-4)(µ-σ : σ′ : η5C2B9H7Me2)(CO)8]

4-Iodobenzylidyne as a precursor ligand for extended unsaturated alkylidyne ligands

Contact Info

Product

Resources

About

Chemistry of polynuclear metal complexes with bridging carbene or carbyne ligands. Part 86. Aikylidyne(carbaborane)molybdenum–gold, –rhodium and –iron complexes; crystal structure of [NEt₄][MoFe₂(µ₃-CC₆H₄Me-4)(µ-σ : σ′ : η⁵C₂B₉H₇Me₂)(CO)₈]