Chemistry of di- and tri-metal complexes with bridging carbene or carbyne ligands. Part 14. Triangulo-metal complexes containing tungsten with iron, cobalt, rhodium, or nickel and a capping tolylidyne ligand; crystal structure of the complex [RhFeW(µ3-CC6H4Me-4)(µ-CO)(CO)5(η-C5H5)(η-C9H7)]

Self Cite

“…8 The "P-{'Hf n.m.r. data for compounds (7)- (10) are similar to those of (1). There are two signals in each spectrum corresponding to the PPt and PW groups present in these complexes.…”

Section: Since ( I ) Was a Key Compound For Further Investigations Itsupporting

confidence: 76%

Chemistry of di- and tri-metal complexes with bridging carbene or carbyne ligands. Part 21. Reactivity of µ-(methoxy-p-tolylmethylene) and µ-(p-tolylmethylidyne) groups at a platinum–tungsten centre. X-Ray crystal structure of [PtW{µ-C(OMe)C₆H₄Me-4}(µ-Ph₂PCH₂PPh₂)(CO)₅]

Mead¹,

Moore²,

Stone³

et al. 1983

Self Cite

“…50%). 4 Despite the presence in the precursor of the Rh(q-C9H7) group, the process requires 1 or 2 d for completion. Moreover, side-reactions must occur to account for the formation of (2) as the major product.…”

Section: Resultsmentioning

confidence: 99%

Chemistry of di- and tri-metal complexes with bridging carbene or carbyne ligands. Part 32. Reactions of the rhodium–tungsten complex [RhW(µ-CC₆H₄Me-4)(CO)₃(η-C₅H₅)(η-C₉H₇)] with alkynes; X-ray crystal structure of [RhW{µ-C(C₆H₄Me-4)C(Ph)C(Ph)}(CO)₂(η-C₅H₅)(η-C₉H₇)]

Green¹,

Howard²,

Porter³

et al. 1984

Self Cite

BS8 I TSThe bimetal compound [RhW(p-CR)(CO),(q-C,H,)(q-C,H,)] (R = C,H,Me-4, C9H7 = indenyl) reacts with the alkynes R 1 C X R 2 (R1 = R2 = Ph or Me; R1 = Ph, R2 = H or Me) in toluene at ca. 50-80 "C to give the bridged complexes [RhW{p-C(R)C(R1)C(R2)](C0)2(q-C5H5)(q-CgH7)]. The molecular structure of the species obtained from PhCrCPh was established by a single-crystal X-ray diffraction study. A] is bridged by a three-carbon chain [mean C-C 1.439(8) A]. Whereas all the atoms of the chain are bound to the rhodium [2.105(6), 2.135(6), and 2.103(5) A], only the two end carbons are attached to the tungsten [2.175(5) and 2.196(6) A]. The tungsten atom carries two essentially orthogonal terminal carbonyl groups, as well as the cyclopentadienyl ring. The indenyl group is asymmetrically attached to the rhodium atom, with three short Rh-C [2.185(7), 2.198(7), and 2.204(7) A] and two long Rh-C [2.334(7) and 2.330( 7) A] separations to the C5 ring, implying slippage towards an +-bonding mode. Formation of [RhW{p-C( R)C(Ph)C(Ph))( C0),(q-C5H5)-(q -C5Me5)] from [ R hW (p-CR) (CO),(q-C5H5) (q-C5Me5)] and PhCXPh requires forcing conditions (1 00 "C, 5 d in toluene), and side-reactions occur to yield hexaphenylbenzene, [Rh(CO),(q-C,Me,)], and the tetraphenylcyciopentadienone complex [ Rh(p-C,Ph,CO) (q-C5Me5)]. The reaction between [RhW(p-CR) (CO),(q-C5H5)(q-C9H7)] and [W(XR)(CO),(q-C5H5)] has also been investigated.With heptane as solvent, the products are the trimetal complex [Rh2W(p3-CR)(p-CO) (CO),(q-C5H5) -(q-C9H7) J, the alkyne-bridged complex [W,(p-RC2R) (CO),( q-C5H5) ,I, and a compound formulated as [W2{p-C(R)C(O)C(R)}(CO),(q-C5H5),]. Spectroscopic data (i.r., H and 13C-{l H) n.m.r.) for the new compounds are reported and discussed.

“…A dark red band was collected, Table 4. Atomic positional (fractional co-ordinates) parameters ( x lo4) with estimated standard deviations in parentheses for -810 ( 12) Table 5. Atomic positional (fractional co-ordinates) parameters ( x lo4) with estimated standard deviations in parentheses for…”

Section: [W('cc6h4me-4)(co)2(q-csh5)120 [Re2(c1-br)2(thf)2(c0)]7mentioning

confidence: 99%

Chemistry of di- and tri-metal complexes with bridging carbene or carbyne ligands. Part 29. Synthesis of rhenium–tungsten compounds; X-ray crystal structures of [ReW₂(µ-Br)(µ-L)(µ-CC₆H₄Me-4)(µ₃-CC₆H₄Me-4)(CO)₃(η-C₅H₅)₂](L = CO or O)

Carriedo¹,

Jeffery²,

Stone³

1984

Self Cite

The compound [W(rCR)(CO),(q-C,H,)] (R = C6H,Me-4) reacts with the rhenium compounds [ Re,(CO) 0] , [ Re2(p-Br),(thf)z(CO)s] (thf = tetrahydrofuran), and [ ReBr( NCMe),(CO),] to afford, respectively, the cluster complexes [ Re2W (p3-C R) (CO) (q-C5 HThe latter compound has been structurally characterrsed by an X-ray diffraction study. A ReW, triangle of metal atoms [W-w 2.620( 1 ), Re-W 2.867(1) and 2.91 2( 1 ) A] is asymmetrically capped by a CC6H,Me-4 ligand [p3-C-Re 2.248(12), p3-C-W 2.035(14) and 2.050(11) A], and is edge-bridged by CC6H4Me-4, Br, and CO groups, with the latter being asymmetrically bound [W-C-0 155(1)"]. The two tungsten atoms carry cyclopentadienyl ligands, and the rhenium atom three terminally bound CO groups. The compound [ ReW,(p-Br))2] which was also characterised by X-ray diffraction. This complex is structurally similar to its precursor but with the significant differences of the p-CO ligand being replaced by p -0 and the capping CC6H4Me-4 being very asymmetrically bound to the metal triangle [p3-C-Re 2.51 5(20), p3-C-W 2.01 7( 19) and 2.7 74( 7 8)A]. In addition to reacting with oxygen, the compound [reacts with sulphur. The nature of the product is described, and the n.m.r. spectra ('H and l3C-(l H)) of all the new compounds are reported and discussed in relation to their established or proposed structures.In a variety of reactions using the tolylmethylidynetungsten compound [W(XR)(C0)2(q-C5H5)] (R = C6H4Me-4) we have described the preparation of trimetal cluster complexes with core structures M2W(p3-CR) (closo with M = Mo, W, Fe, Co, or Rh; butterfly with Pt or Cu), MM'W(p3-CR) (closo with M = Fe, M' = Co, Rh, or Pt; butterfly with M = Pt, M' = = Cu), MW2(p-CR)2 (M = Ni, Pd, Pt, Ag, or Au), MW2[~3-(q2-I_)RC2Rl (M = Fe), and MW[p3-(q2-II)-RC2R] (M = Ru or OS).*-~ However, we have not as yet described trimetal clusters derived from [W(3ZR)(C0)2(q-C5Hs)] and involving the elements manganese or rhenium. In this paper we report some cluster compounds with rheniumtungsten bonds and bridging p-CR and p3-CR groups. Results and DiscussionBased on the isolobal r n ~d e l , ~ and our previous synthesis of the cluster compound [COZW(~~-CR)(CO)~(~-CSH~)] (R = C6H4Me-4),4 the trimetal complex [Re2W(p3-CR)(CO)l~-(q-C5H5)] would be expected to exist because of the relationships (i). Unlike [Co2(CO),], however, decarbonyldirhenium is relatively inert. For example, it does not readily react with alkynes as does the dicobalt species. Since there is a similarity between the reactivity patterns of [W(XR)(CO)2(q-CsH5)] * 1,2-p-Bromo-l,3-~-carbonyl-and 1,2-p-bromo-l,3-poxo-l, 1,ltricarbonyl-2,3-bis(q-cyclopen tadienyl)-2,3-p-p-tolylmethylidyne-p3-p-tolylmet hylidyne-triangulo-rheniumditungsten. Supplementary data available (No. SUP 23919, 55 pp.