Oraliq metall nitril kompleksi sahifasining manbasini koʻrish

[[Fayl:Tetrakis(acetonitrile)copper(I)_hexafluorophosphate.png|right|thumb| [Cu(MeCN) <sub>4</sub> ] <sup>+</sup>, tez-tez PF <sub>6</sub> <sup>-</sup> tuzi sifatida uchraydi, keng tarqalgan oʻtish metall nitril kompleksidir.]]
'''Oʻtish metallining nitril komplekslari''' nitril ligandlarini oʻz ichiga olgan koordinatsion birikmalardir . Nitrillar zaif asosli boʻlganligi sababli, bu komplekslardagi nitril ligandlari koʻpincha labildir .<ref>{{Jurnal manbasi|last=Rach, S. F.; Kühn, F. E.|title=Nitrile Ligated Transition Metal Complexes with Weakly Coordinating Counteranions and Their Catalytic Applications|url=https://archive.org/details/sim_chemical-reviews_2009-05-13_109_5/page/2061|journal=Chemical Reviews|year=2009|volume=109|issue=5|pages=2061–2080|doi=10.1021/cr800270h|pmid=19326858}}</ref>

== Nitrillarning qoʻllanishi ==
Odatda nitril ligandlari asetonitril, propionitril va benzonitrildir . [Ru(NH<sub>3</sub>)<sub>5</sub> (NCPh)] <sup>n+</sup> tuzilmalari 2+ va 3+ oksidlanish darajalari uchun aniqlangan. Oksidlanishdan keyin Ru-NH <sub>3</sub> masofalari qisqaradi va Ru-NCPh masofalari uzayadi, bu sof sigma donor ligandlari vazifasini bajaradigan aminlar va pi-akseptorlari sifatida ishlaydigan nitrillarga mos keladi.<ref>{{Jurnal manbasi|doi=10.1021/ic9700967|title=Electronic and Molecular Structures of Pentaammineruthenium Pyridine and Benzonitrile Complexes as a Function of Oxidation State|year=1997|last=Shin|first1=Yeung-gyo K.|last2=Szalda|first2=David J.|last3=Brunschwig|first3=Bruce S.|last4=Creutz|first4=Carol|last5=Sutin|first5=Norman|journal=Inorganic Chemistry|volume=36|issue=14|pages=3190–3197|pmid=11669976}}</ref>
[[Fayl:A5Ru(NCPh).png|right|thumb| 2+ va 3+ tuzlar uchun [Ru(NH <sub>3</sub> ) <sub>5</sub> (NCPh)] <sup>n+</sup> ning strukturaviy taqqoslashlari (pikometrlardagi masofa)]]

== Sintez va reaksiyalar ==
Asetonitril, propionitril va benzonitril ham mashhur erituvchilardir. Nitril [[erituvchilar]] yuqori dielektrik oʻtkazuvchanlikka ega boʻlganligi sababli, nitril ligandini oʻz ichiga olgan katyonik komplekslar koʻpincha ushbu nitril eritmasida eriydi.

Ayrim komplekslarni suvsiz metall tuzini nitrilda eritib tayyorlash mumkin. Boshqa hollarda, metall suspenziyasi nitrildagi NOBF <nowiki><sub id="mwKw">4</sub></nowiki> eritmasi bilan oksidlanadi:<ref>{{Jurnal manbasi|doi=10.1002/0471224502.ch2|journal=Inorg. Synth.|volume=33|pages=75–83|title=Homoleptic Transition Metal Acetonitrile Cations with Tetrafluoroborate or Trifluoromethanesulfonate Anions|first1=Robert A.|last=Heintz|first2=Jennifer A.|last2=Smith|first3=Paul S.|last3=Szalay|first4=Amy|last4=Weisgerber|first5=Kim R.|last5=Dunbar|year=2002}}</ref>

: Ni + 6 MeCN + 2 NOBF <sub>4</sub> → [Ni(MeCN) <sub>6</sub> ](BF <sub>4</sub> ) <sub>2</sub> + 2 NO

Molibden va volframning geteroleptik komplekslari ularning tegishli geksakarbonil komplekslaridan sintezlanishi mumkin.<ref>{{Jurnal manbasi|doi=10.1002/9780470132593.ch14|journal=[[Inorganic Syntheses]]|volume=28|pages=63–67|title=Acetonitrile Complexes of Selected Transition Metal Cations|first1=Richard R.|last=Thomas|first2=Ayusman|last2=Sen|year=2007|isbn=9780470132593}}</ref>

: M(CO) <sub>6</sub> + 4 MeCN + 2 NOBF <sub>4</sub> → [M(NO) <sub>2</sub> (MeCN) <sub>4</sub> ](BF <sub>4</sub> ) <sub>2</sub>

[[Fayl:ACNNIZ.png|left|thumb| [Ni(MeCN) <sub>6</sub> ] <sup>2+</sup> <ref>{{Jurnal manbasi|doi=10.1107/S0567740876006249|journal=Acta Crystallographica Section B|year=1976|last=I. Sotofte|last2=R. G. Hazell|last3=S. E. Rasmussen|volume=32|pages=1692–1696|title=Hexaacetonitrilenickel(II) Tetrachlorozincate. A Crystal Structure with Serious Overlap in the Patterson Function|issue=6}}</ref> ning tetraklorozinkat (ZnCl <sub>4</sub> <sup>2−</sup> ) tuzi strukturasining qismi.]]
Ayrim asetonitril komplekslarini sintez qilish uchun nitril qaytaruvchi vazifasini bajaradi. Bu usul molibden pentakloridning molibden (IV) kompleksiga aylanishi bilan tasvirlangan:<ref>{{Kitob manbasi|series=Inorganic Syntheses|chapter=The Synthesis of Molybdenum and Tungsten Dinitrogen Complexes|year=1990|doi=10.1002/9780470132593.ch7|last=Dilworth|first=Jonathan R.|title=Inorganic Syntheses|pages=33–43|isbn=9780470132593}}</ref>

: 2 MoCl <sub>5</sub> + 5 CH <sub>3</sub> CN → 2 MoCl <sub>4</sub> (CH <sub>3</sub> CN) <sub>2</sub> + ClCH <sub>2</sub> CN + HCl

=== Reaksiyalar ===
Oʻtish metallining nitril komplekslari odatda qoʻllanadi, chunki nitril ligand labil va nisbatan kimyoviy inertdir. Biroq, katyonik nitril komplekslari uglerodga nukleofil hujumga moyil. Shunday qilib, baʼzi nitril komplekslari amidlarni berish uchun nitrillarning gidrolizlanishini katalizlaydi.<ref>{{Kitob manbasi|doi=10.1016/B0-08-043748-6/01248-2|chapter=Reactivity of Coordinated Nitriles|title=Comprehensive Coordination Chemistry II|year=2003|last=Pombeiro|first=A.J.L.|pages=639–660|isbn=9780080437484}}</ref>

Fe- va Co-nitril komplekslari nitrilgidrataz fermentlarining oraliq mahsulotidir. N-koordinatsiyasi sp-gibridlangan uglerod markazini nukleofillar, shu jumladan suv tomonidan hujumga olib keladi.<ref>{{Jurnal manbasi|doi=10.1021/ja00315a029|title=Synthesis and base hydrolysis of pentaammine N,N-dimethylformamide and acetonitrile complexes of rhodium(III) and iridium(III)|url=https://archive.org/details/american-chemical-society-journal_1984-02-08_106_3/page/625|year=1984|last=Curtis|first1=Neville J.|last2=Sargeson|first2=Alan M.|journal=Journal of the American Chemical Society|volume=106|issue=3|pages=625–630}}</ref> Shunday qilib, nitrilning katyonik metall markaziga koordinatsiyasi katalitik gidratsiya uchun asosdir:

: M-NCR + H <sub>2</sub> O → MO=C(NH <sub>2</sub> )R
: MO=C(NH <sub>2</sub> )R + NCR → O=C(NH <sub>2</sub> )R + M-NCR

== Misollar ==

=== [M(NCMe) <sub>6</sub> ] <sup>n+</sup> ===

* Hexakis(asetonitril)vanadiy(II) tetraxlorzinkat ([V(MeCN) <sub>6</sub> ](ZnCl <sub>4</sub> ) <sub>2</sub> ), yashil <ref>{{Jurnal manbasi|doi=10.1016/j.ica.2004.10.037|title=A Study of the 8466 Structures Reported in Inorganica Chimica Acta: 52 Space Group Changes and Their Chemical Consequences|year=2005|last=Clemente|first1=Dore Augusto|journal=Inorganica Chimica Acta|volume=358|issue=6|pages=1725–1748}}</ref>
* Hexakis(asetonitril)xrom(II) bis(tetrafenilborat) ([Cr(MeCN) <sub>6</sub> ](B(C <sub>6</sub> H <sub>5</sub> ) <sub>4</sub> ) <sub>2</sub>, yashil <ref>{{Jurnal manbasi|doi=10.1107/S2053229615015739|title=An Investigation of the Electron Density of a Jahn–Teller-Distorted Cr<sup>II</sup> Cation: The Crystal Structure and Charge Density of Hexakis(acetonitrile-κN)chromium(II) Bis(tetraphenylborate) Acetonitrile Disolvate|year=2015|last=Thangavel|first1=Arumugam|last2=Wieliczko|first2=Marika|last3=Scarborough|first3=Christopher|last4=Dittrich|first4=Birger|last5=Bacsa|first5=John|journal=Acta Crystallographica Section C Structural Chemistry|volume=71|issue=11|pages=936–943|pmid=26524164}}</ref>
* Hexakis(asetonitril)xrom(III) tetrafloroborat ([Cr(MeCN) <sub>6</sub> ](BF <sub>4</sub> ) <sub>3</sub> ), oq <ref>{{Jurnal manbasi|doi=10.1016/j.jpcs.2003.08.020|title=Synthesis and Characterization of Hexakis(acetonitrile)chromium(III) Tetrafluoroborate, &#91;Cr<sup>III</sup>(NCMe)<sub>6</sub>&#93;&#91;BF<sub>4</sub>&#93;3. A Nonaqueous Cr<sup>III</sup> Source|url=https://archive.org/details/sim_journal-of-physics-and-chemistry-of-solids_2004-01_65_1/page/61|year=2004|last=Hatlevik|first1=Øyvind|last2=Arif|first2=Atta M.|last3=Miller|first3=Joel S.|journal=Journal of Physics and Chemistry of Solids|volume=65|pages=61–63}}</ref>
* Hexakis(asetonitril)temir(II) bis(tetrakis(pentaflorofenil)borat) ([Fe(MeCN) <sub>6</sub> ](B(C <sub>6</sub> F <sub>5</sub> ) <sub>4</sub> ) <sub>2</sub>, apelsin <ref>{{Jurnal manbasi|doi=10.1039/C7DT04593J|title=New Reactivity at the Silicon Bridge in Sila&#91;1&#93;ferrocenophanes|year=2018|last=Musgrave|first1=Rebecca A.|last2=Hailes|first2=Rebekah L. N.|last3=Schäfer|first3=André|last4=Russell|first4=Andrew D.|last5=Gates|first5=Paul J.|last6=Manners|first6=Ian|journal=Dalton Transactions|volume=47|issue=8|pages=2759–2768|pmid=29417116|url=https://research-information.bris.ac.uk/ws/files/144073031/accepted_manuscript.pdf}}</ref>
* Hexakis(asetonitril)kobalt(II) bis(tetrakis(pentafluorofenil)borat) ([Co(MeCN) <sub>6</sub> ](B(C <sub>6</sub> F <sub>5</sub> ) <sub>4</sub> ) <sub>2</sub>, binafsha <ref>{{Jurnal manbasi|doi=10.1002/ejic.200800201|title=Synthesis and Characterization of Acetonitrile-Ligated Transition-Metal Complexes with Tetrakis(pentafluorophenyl)borate as Counteranions|year=2008|last=Hijazi|first1=Ahmed K.|last2=Al Hmaideen|first2=Akef|last3=Syukri|first3=Syukri|last4=Radhakrishnan|first4=Narayanan|last5=Herdtweck|first5=Eberhardt|last6=Voit|first6=Brigitte|last7=Kühn|first7=Fritz E.|journal=European Journal of Inorganic Chemistry|volume=2008|issue=18|pages=2892–2898}}</ref>
* Hexakis(asetonitril)nikel(II) tetrafloroborat ([Ni(MeCN) <sub>6</sub> ](BF <sub>4</sub> ) <sub>2</sub> ), koʻk
* Hexakis(asetonitril)mis(II) bis(tetrakis(pentaflorofenil)borat) ([Cu(MeCN) <sub>6</sub> ](B(C <sub>6</sub> F <sub>5</sub> ) <sub>4</sub> ) <sub>2</sub>, och koʻk-yashil qattiq <ref>{{Jurnal manbasi|doi=10.1002/marc.200600139|title=Isobutene Polymerization Using &#91;CuII(NCMe)6&#93;2+ with Non-Coordinating Anions as Catalysts|year=2007|last=Hijazi|first1=Ahmed K.|last2=Yeong|first2=Hui Y.|last3=Zhang|first3=Yanmei|last4=Herdtweck|first4=Eberhardt|last5=Nuyken|first5=Oskar|last6=Kühn|first6=Fritz E.|journal=Macromolecular Rapid Communications|volume=28|issue=5|pages=670–675}}</ref>
* Hexakis(asetonitril)rutenium (II) tetrafloroborat ([Ru(MeCN) <sub>6</sub> ](BF <sub>4</sub> ) <sub>2</sub> ), oq, d <sub>Ru-N</sub> = 202 pm.<ref>{{Jurnal manbasi|doi=10.1016/j.ica.2013.02.027|title=Synthesis and Electrochemical characterization of &#91;Ru(NCCH<sub>3</sub>)<sub>6</sub>&#93;<sup>2+</sup>, Tris(acetonitrile) Tris(pyrazolyl)borate, and Tris(acetonitrile) Tris(pyrazolyl)methane Ruthenium(II) Complexes|year=2013|last=Underwood|first1=Christopher C.|last2=Stadelman|first2=Bradley S.|last3=Sleeper|first3=Mark L.|last4=Brumaghim|first4=Julia L.|journal=Inorganica Chimica Acta|volume=405|pages=470–476}}</ref>
* Hexakis(asetonitril)rodiy(III) tetrafloroborat ([Rh(MeCN) <sub>6</sub> ](BF <sub>4</sub> ) <sub>3</sub> ), sariq rangli qattiq modda.<ref name="KimD">{{Jurnal manbasi|doi=10.1021/ja991130e|title=A Remarkable Family of Rhodium Acetonitrile Compounds Spanning Three Oxidation States and with Nuclearities Ranging from Mononuclear and Dinuclear to One-Dimensional Chains|url=https://archive.org/details/american-chemical-society-journal_1999-09-08_121_35/page/8005|year=1999|last=Prater|first1=M. E.|last2=Pence|first2=L. E.|last3=Clérac|first3=R.|last4=Finniss|first4=G. M.|last5=Campana|first5=C.|last6=Auban-Senzier|first6=P.|last7=Jérome|first7=D.|last8=Canadell|first8=E.|last9=Dunbar|first9=K. R.|journal=Journal of the American Chemical Society|volume=121|issue=35|pages=8005–8016}}</ref>

=== [M(NCMe) <sub>4</sub> ] <sup>n+</sup> ===

* [Cr(MeCN) <sub>4</sub> ](BF <sub>4</sub> ) <sub>2</sub>, koʻk <ref>{{Jurnal manbasi|doi=10.1039/A708988K|title=Synthesis, characterization, and reactions of tetrakis(nitrile)chromium(II) tetrafluoroborate complexes †|year=1998|last=Henriques|first1=Rui T.|last2=Herdtweck|first2=Eberhardt|last3=Kühn|first3=Fritz E.|last4=Lopes|first4=André D.|last5=Mink|first5=Janos|last6=Romão|first6=Carlos C.|journal=Journal of the Chemical Society, Dalton Transactions|issue=8|pages=1293–1298}}</ref>
* [Cu(MeCN) <nowiki><sub id="mwsw">4</sub></nowiki> ]PF <nowiki><sub id="mwtA">6</sub></nowiki>, rangsiz
* [Pd(MeCN) <sub>4</sub> ](BF <sub>4</sub> ) <sub>2</sub>, sariq <ref>{{Kitob manbasi|doi=10.1002/9780470132593.ch14|chapter=Acetonitrile Complexes of Selected Transition Metal Cations|series=Inorganic Syntheses|year=1990|last=Thomas|first=Richard R.|title=Inorganic Syntheses|pages=63–67|isbn=9780470132593}}</ref>

=== [M(NCMe) <sub>4 yoki 5</sub> ] <sub>2</sub> <sup>n+</sup> ===

* [Mo <sub>2</sub> (MeCN) <sub>8/10</sub> ](BF <sub>4</sub> ) <sub>4</sub> koʻk d(Mo-Mo) = 218, d(Mo-N) <sub>eksenel</sub> = 260, d(Mo-N) <sub>tenglama</sub> = 214 pm <ref>{{Jurnal manbasi|doi=10.1021/ic00004a055|title=Synthesis and characterization of octaacetonitriledimolybdenum(II) tetrafluoroborate|year=1991|last=Cotton|first1=F. Albert.|last2=Wiesinger|first2=Kenneth J.|journal=Inorganic Chemistry|volume=30|issue=4|pages=871–873}}</ref>
* [Tc <sub>2</sub> (MeCN) <sub>10</sub> ](BF <sub>4</sub> ) <sub>4</sub> <ref>{{Jurnal manbasi|doi=10.1021/ic00111a040|title=Preparation and Characterization of the Fully Solvated Ditechnetium Cation &#91;Tc<sub>2</sub>(CH<sub>3</sub>CN)<sub>10</sub>&#93;<sup>4+</sup>|year=1995|last=Bryan|first1=Jeffrey C.|last2=Cotton|first2=F. Albert|last3=Daniels|first3=Lee M.|last4=Haefner|first4=Steven C.|last5=Sattelberger|first5=Alfred P.|journal=Inorganic Chemistry|volume=34|issue=7|pages=1875–1883}}</ref>
* [Re <sub>2</sub> (MeCN) <sub>10</sub> ][B(C <sub>6</sub> H <sub>3</sub> (CF <sub>3</sub> ) <sub>2</sub> ) <sub>4</sub> ] <sub>2</sub>,<ref>{{Jurnal manbasi|doi=10.1039/b601463a|title=Syntheses and Reactivity Studies of Solvated Dirhenium Acetonitrile Complexes|url=https://archive.org/details/sim_dalton-transactions_2006-09-07_33/page/4011|year=2006|last=Bera|first1=Jitendra K.|last2=Schelter|first2=Eric J.|last3=Patra|first3=Sanjib K.|last4=Bacsa|first4=John|last5=Dunbar|first5=Kim R.|journal=Dalton Transactions|issue=33|pages=4011–9|pmid=17028710}}</ref> koʻk; d(Re-Re) = 226, d(Re-N) <sub>eksenel</sub> = 240, d(Re-N) <sub>tenglama</sub> = 205 pm
* [Rh <sub>2</sub> (MeCN) <sub>10</sub> ](BF <sub>4</sub> ) <sub>4</sub>, apelsin; d(Rh-Rh) = 261, d(Re-N) <sub>eksenel</sub> = 219, d(Re-N) <sub>tenglama</sub> = 198 pm <ref name="KimD"/>

=== Boshqa diqqatga sazovor misollar ===

* Bis(benzonitril)palladiy diklorid (PdCl <sub>2</sub> (PhCN) <sub>2</sub> ), "PdCl <sub>2</sub> " manbai boʻlib xizmat qiluvchi toʻq sariq rangli qattiq modda.
* Trikarboniltris(propionitril)molibden(0) (Mo(CO) <sub>3</sub> (C <sub>2</sub> H <sub>5</sub> CN) <sub>3</sub> ), "Mo(CO) <sub>3</sub> " manbai. Tegishli Cr va W komplekslari maʼlum.<ref>{{Kitob manbasi|chapter=Tricarbonyltris(Nitrile) Complexes of Cr, Mo, and W|year=1990|first=Gregory J.|last=Kubas|title=Inorganic Syntheses|series=Inorganic Syntheses|pages=29–33|doi=10.1002/9780470132593.ch6|isbn=9780470132593}}</ref>

== <math>\eta</math><sup>2</sup> -nitril ligandlarining komplekslari ==
Uning ayrim komplekslarida nitrillar <math>\eta</math><sup>2</sup> -ligandlar vazifasini bajaradi. Bu bogʻlanish rejimi Ni(0) kabi past valentli metallar komplekslari uchun koʻproq uchraydi..<math>\eta</math><sup>2</sup> -nitril komplekslari nitrillarning ba'zi metall katalizlangan reaktsiyalarida, masalan, Hoesch reaktsiyasi va nitrillarning gidrogenatsiyasida vaqtinchalik oraliq mahsulotlar sifatida hosil boʻlishi kutilmoqda. Baʼzi hollarda, <math>\eta</math><sup>2</sup> -nitril ligandlari oksidlovchi qoʻshilishdan oldin boʻlgan oraliq mahsulotlardir.<ref>{{Jurnal manbasi|last=Churchill, D.|last2=Shin, J. H.|last3=Hascall, T.|last4=Hahn, J. M.|last5=Bridgewater, B. M.|last6=Parkin, G.|title=The Ansa Effect in Permethylmolybdenocene Chemistry: A [Me<sub>2</sub>Si] Ansa Bridge Promotes Intermolecular C−H and C−C Bond Activation|journal=Organometallics|year=1999|volume=18|pages=2403–2406|doi=10.1021/om990195n}}</ref>
[[Fayl:ACEKAU.png|thumb|220x220px| Ni( difosfin )(ē <sup>2</sup> - PhCN ) ning tuzilishi <ref>{{Jurnal manbasi|last=García, J. J.; Arévalo, A.; Brunkan, N. M.; Jones, W. D.|title=Cleavage of Carbon−Carbon Bonds in Alkyl Cyanides Using Nickel(0)|journal=Organometallics|year=2004|volume=23|issue=16|pages=3997–4002|doi=10.1021/om049700t}}</ref>]]

== Yana qarang ==

* Siyanometalat - siyanid ligandlarini oʻz ichiga olgan koordinatsion birikmalar (C orqali muvofiqlashtiruvchi).

== Manbalar ==
<references />

[[Turkum:Koordinatsion birikmalar]]