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transition metal alkyne complex wikipedia jump to content main menu main menu move to sidebar hide navigation main page contents current events random article about wikipedia contact us contribute help learn to edit community portal recent changes upload file special pages search search appearance donate create account log in personal tools donate create account log in contents move to sidebar hide top 1 synthesis 2 reactions 3 structure and bonding toggle structure and bonding subsection 3 1 η 2 coordination to a single metal center 3 2 η 2 η 2 coordination bridging two metal centers 3 3 benzyne complexes 4 applications 5 references toggle the table of contents transition metal alkyne complex 2 languages čeština 日本語 edit links article talk english read edit view history tools tools move to sidebar hide actions read edit view history general what links here related changes upload file permanent link page information cite this page get shortened url switch to legacy parser print export download as pdf printable version in other projects wikidata item appearance move to sidebar hide from wikipedia the free encyclopedia redirected from semihydrogenation in organometallic chemistry a transition metal alkyne complex is a coordination compound containing one or more alkyne ligands such compounds are intermediates in many catalytic reactions that convert alkynes to other organic products e g hydrogenation and trimerization 1 they are distinct from acetylide complexes synthesis edit transition metal alkyne complexes are often formed by the displacement of labile ligands by the alkyne for example a variety of cobalt alkyne complexes arise by the reaction of alkynes with dicobalt octacarbonyl 2 co 2 co 8 r 2 c 2 r 2 c 2 co 2 co 6 2 co many alkyne complexes are produced by reduction of metal halides 3 cp 2 ticl 2 mg me 3 sic csime 3 cp 2 ti csime 3 2 mgcl 2 complexes of dichloroacetylene are produced by in situ reduction of the metal by the alkyne 4 4 c 2 cl 2 2 wcl 6 wcl 4 c 2 cl 2 2 2 c 2 cl 4 reactions edit transition metal alkyne complexes participate in many reactions protonation of alkyne ligands gives alkenyl complexes lnm rc cr h lnm cr crh complexes of terminal alkenes are prone to rearrange to vinylidene derivatives lnm hc cr lnm c crh the pauson khand reaction provides a route to cyclopentenones via the intermediacy of cobalt alkyne complexes pk reaction structure and bonding edit structures of various metal alkyne complexes the coordination of alkynes to transition metals is similar to that of alkenes the bonding is described by the dewar chatt duncanson model upon complexation the c c bond elongates and the alkynyl carbon bends away from 180º for example in the phenylpropyne complex pt pph 3 2 mec 2 ph the c c distance is 1 277 25 vs 1 20 å for a typical alkyne the c c c angle distorts 40 from linearity upon complexation 5 because the bending induced by complexation strained alkynes such as cycloheptyne and cyclooctyne are stabilized by complexation 6 the c c vibration of alkynes occurs near 2300 cm 1 in the ir spectrum this mode shifts upon complexation to around 1800 cm 1 indicating a weakening of the c c bond η 2 coordination to a single metal center edit when bonded side on to a single metal atom an alkyne serves as a dihapto usually two electron donor for early metal complexes e g cp 2 ti c 2 r 2 strong π backbonding into one of the π antibonding orbitals of the alkyne is indicated this complex is described as a metallacyclopropene derivative of ti iv for late transition metal complexes e g pt pph 3 2 mec 2 ph the π backbonding is less prominent and the complex is assigned oxidation state 0 7 8 in some complexes the alkyne is classified as a four electron donor in these cases both pairs of pi electrons donate to the metal this kind of bonding was first implicated in complexes of the type w co r 2 c 2 3 9 η 2 η 2 coordination bridging two metal centers edit because alkynes have two π bonds alkynes can form stable complexes in which they bridge two metal centers the alkyne donates a total of four electrons with two electrons donated to each of the metals and example of a complex with this bonding scheme is η 2 diphenylacetylene hexacarbonyl dicobalt 0 8 benzyne complexes edit transition metal benzyne complexes represent a special case of alkyne complexes since the free benzynes are not stable in the absence of the metal 10 applications edit metal alkyne complexes are intermediates in the semi hydrogenation of alkynes to alkenes 11 c 2 r 2 h 2 cis c 2 r 2 h 2 this transformation is conducted on a large scale in refineries which unintentionally produce acetylene during the production of ethylene it is also useful in the preparation of fine chemicals semihydrogenation affords cis alkenes 12 metal alkyne complexes are also intermediates in the metal catalyzed trimerization and tetramerizations cyclooctatetraene is produced from acetylene via the intermediacy of metal alkyne complexes acrylic acid was once prepared by the hydrocarboxylation of acetylene 13 c 2 h 2 h 2 o co h 2 c chco 2 h with the shift away from coal based acetylene to petroleum based feedstocks olefins catalytic reactions with alkynes are not widely practiced industrially polyacetylene has been produced using metal catalysis involving alkyne complexes ti catalyzed polymerization of acetylene inspired by ziegler natta catalysis cuprous chloride also catalyzes the dimerization of acetylene to vinylacetylene once used as a precursor to various polymers such a neoprene mechanistic studies suggest that this reaction proceeds by insertion of acetylene into a copper i acetylide complex 14 references edit elschenbroich c organometallics 2006 wiley vch weinheim isbn 3 527 29390 6 kemmitt r d w russell d r cobalt in comprehensive organometallic chemistry i abel e w stone f g a wilkinson g eds 1982 pergamon press oxford isbn 0 08 025269 9 rosenthal uwe burlakov vladimir v arndt perdita baumann wolfgang spannenberg anke 2003 the titanocene complex of bis trimethylsilyl acetylene synthesis structure and chemistry organometallics 22 5 884 900 doi 10 1021 om0208570 stahl karlheinz weller frank dehnicke kurt 1986 dichloracetylen als stabiler komplexligand die kristallstruktur von pph 4 wcl 5 c 2 cl 2 0 5 ccl 4 zeitschrift für anorganische und allgemeine chemie 533 2 73 82 doi 10 1002 zaac 19865330210 davies b william payne n c 1975 studies on metal acetylene complexes v crystal and molecular structure of bis triphenylphosphine 1 phenylpropyne platinum 0 p c 6 h 5 3 2 c 6 h 5 ccch 3 pt 0 j organomet chem 99 315 doi 10 1016 s0022 328x 00 88462 4 bennett martin a schwemlein heinz p 1989 metal complexes of small cycloalkynes and arynes angew chem int ed engl 28 10 1296 1320 doi 10 1002 anie 198912961 hill a f organotransition metal chemistry 2002 royal society of chemistry isbn 0 471 28163 8 1 2 crabtree r h comprehensive organometallic chemistry v 2009 john wiley sons isbn 978 0 470 25762 3 verification needed joseph l templeton 1989 four electron alkyne ligands in molybdenum ii and tungsten ii complexes advances in organometallic chemistry 29 1 100 doi 10 1016 s0065 3055 08 60352 4 william m jones jerzy klosin transition metal complexes of arynes strained cyclic alkynes and strained cyclic cumulenes advances in organometallic chemistry 1998 volume 42 pages 147 221 doi 10 1016 s0065 3055 08 60543 2 kusy rafał grela karol 2025 renaissance in alkyne semihydrogenation mechanism selectivity functional group tolerance and applications in organic synthesis chemical reviews 125 9 4397 4527 doi 10 1021 acs chemrev 4c00001 pmid 40279298 michaelides i n dixon d j 2013 catalytic stereoselective semihydrogenation of alkynes to e alkenes angew chem int ed 52 3 806 808 doi 10 1002 anie 201208120 pmid 23255528 w bertleff m roeper x sava carbonylation ullmann s encyclopedia of industrial chemistry weinheim wiley vch doi 10 1002 14356007 a05_217 isbn 978 3 527 30673 2 trotuş ioan teodor zimmermann tobias schüth ferdi 2014 catalytic reactions of acetylene a feedstock for the chemical industry revisited chemical reviews 114 3 1761 1782 doi 10 1021 cr400357r pmid 24228942 v t e organometallic chemistry principles crystal field theory ligand field theory 18 electron rule d electron count polyhedral skeletal electron pair theory isolobal principle π backbonding dewar chatt duncanson model hapticity spin states agostic interaction metal ligand multiple bond reactions oxidative addition reductive elimination migratory insertion β hydride elimination transmetalation carbometalation hydrometalation types of compounds gilman reagents grignard reagents cyclopentadienyl complexes transition metal indenyl complexes transition metal fullerene complexes metallocenes metal tetranorbornyls sandwich compounds half sandwich compounds transition metal acyl complexes transition metal carbene complexes transition metal carbyne complexes transition metal alkene complexes transition metal alkyne complexes transition metal allyl complexes transition metal carbides arene complexes of univalent gallium indium and thallium applications carbonylation cativa process grignard reaction monsanto process olefin metathesis shell higher olefin process ziegler natta process related branches of chemistry organic chemistry inorganic chemistry bioinorganic chemistry category v t e coordination complexes h donors h h 2 bh 4 b donors br 2 bh 4 b m h n c donors r rc o hc o ch 2 chch 2 allyl c ch 2 3 ch 2 ch 2 h 2 c ch ch ch 2 cr cr 2 rc 2 r c 6 h 4 cn co co 2 c 4 c 6 r 6 c 60 c 70 rnc cr 2 cr c 5 h 5 c 9 h 7 cs c cr 2 cs 2 si donors h n sir 4 n r 3 si n donors nh 3 h 2 nch 2 ch 2 nh 2 etc n 3 nco imidazole no rno no 2 py amino acid n 3 rn 2 rcn bipy phen porphyrin me 3 si 2 n n 2 ncs p donors pr 3 pf 3 pr 2 pr 2 oh as donors asr 3 bi donors r n bi n rbi o donors h 2 o oh r 2 o ro o 2 o 2 o 2 2 4 co 2 3 hco 3 c 2 o 2 4 rco 2 rconr 2 oc nr 2 2 acac r 2 co ono no 3 clo 4 c 5 h 5 no osr 2 so 2 4 po 3 4 opr 3 s donors r 2 ncs 2 rs hs and h 2 s r 2 s r 2 c 2 s 2 2 so so 2 so 2 3 s 2 o 2 3 sr 2 o ncs cs 2 halide donors f f 2 cl br i retrieved from https en wikipedia org w index php title transition_metal_alkyne_complex oldid 1352245624 applications categories organometallic chemistry transition metal compounds coordination complexes hidden categories all pages needing factual verification wikipedia articles needing factual verification from may 2015 this page was last edited on 3 may 2026 at 01 36 utc page was rendered with parsoid text is available under the creative commons attribution sharealike 4 0 license additional terms may apply by using this site you agree to the terms of use and privacy policy wikipedia is a registered trademark of the wikimedia foundation inc a non profit organization privacy policy about wikipedia disclaimers contact wikipedia legal safety contacts code of conduct developers statistics cookie statement mobile view search search toggle the table of 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