有機白金化合物

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create by mixing or combining
(chemistry) a substance formed by chemical union of two or more elements or ingredients in definite proportion by weight (同)chemical_compound
put or add together; "combine resources" (同)combine
an enclosure of residences and other building (especially in the Orient)
a whole formed by a union of two or more elements or parts
combine so as to form a whole; mix; "compound the ingredients" (同)combine
calculate principal and interest
composed of more than one part; "compound leaves are composed of several lobes; "compound flower heads"
consisting of two or more substances or ingredients or elements or parts; "soap is a compound substance"; "housetop is a compound word"; "a blackberry is a compound fruit"
combined into or constituting a chemical compound

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(…になるように)〈要素・成分など〉'を'混ぜ合わせる《+『名』+『into』+『名』》;(…から)〈薬など〉'を'調合する,混ぜ合わせて作る《+『名』+『from』(『of』)+『名』》 / 《しばしば受動態で》〈めんどうな事・損害など〉'を'もっとひどくする / 〈利子〉'を'複利で計算する / (…と)話し合いをつける,妥協する《+『with』+『名』》 / 複合の,合成の / 『合成物』,混合物,調合物;化合物 / 複合語,合成語(classroom, heart-to-heartなどをいう)
(異民族の家屋・商館などがある)囲み地区,構内

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出典(authority):フリー百科事典『ウィキペディア（Wikipedia）』「2016/11/23 20:12:10」(JST)

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Organoplatinum chemistry is the chemistry of organometallic compounds containing a carbon to platinum chemical bond, and the study of platinum as a catalyst in organic reactions.^[1]^[2]^[3] Organoplatinum compounds exist in oxidation state 0 to IV, with oxidation state II most abundant. The general order in bond strength is Pt-C (sp) > Pt-O > Pt-N > Pt-C (sp³). Organoplatinum and organopalladium chemistry are similar, but organoplatinum compounds are more stable and therefore less useful as catalysts.

Organoplatinum(0)

Most organoplatinum(0) compounds contain alkene and alkyne ligands. Carbonyl complexes are rare, and the analogue of Ni(CO)₄ is elusive. The alkene and alkyne ligands serve as two-electron donors, for example in the complexes (PPh₃)₂Pt(C₂H₄) and (PPh₃)₂Pt(C₂Ph₂). The ethylene ligand in (PPh₃)₂Pt(C₂H₄) is labile and exchanges with alkynes and electrophilic alkenes, even C₆₀ a fullerene.

A general synthetic route to (PPh₃)₂Pt(un) (un = alkene, alkyne) is reduction of potassium tetrachloroplatinate with ethanolic potassium hydroxide or hydrazine in presence of a phosphine ligand such as triphenylphosphine and the alkene or alkyne. Such reactions proceed via the intermediacy of cis-dichlorobis(triphenylphosphine)platinum(II). Nitrogen-based ligands do not often support the formation of platinum complexes of alkenes and alkynes.

Zerovalent organoplatinum complexes lacking phosphine ligands are often prepared via PtCl₂(COD).

Li₂C₈H₈ + PtCl₂(COD) + 3 C₇H₁₀ → [Pt(C₇H₁₀)₃] + 2 LiCl + C₈H₈ + C₈H₁₂

Pt(C₇H₁₀)₃ + 2 COD → Pt(COD)₂ + 3 C₇H₁₀

where C₇H₁₀ is norbornene.

Organoplatinum(I)

Platinum(I) compounds are uncommon but generally are diamagnetic because they have Pt-Pt bonds. An example is the dication [Pt₂(CO)₆]²⁺.

Organoplatinum(II)

A historically significant organoplatinum(II) compound is Zeise's salt, which is obtained from ethylene and potassium tetrachloroplatinate:

The colourless diolefin complex dichloro(cycloocta-1,5-diene)platinum(II) is a more modern relative, and is more widely used.

The stability and diversity of platinum(II) alkene complexes contrasts with the rarity of alkene complexes of nickel(II). Platinum allyl complexes are also common. In contrast to nickel chemistry, where compounds such as CpNi(L)X are common, cyclopentadienyl derivatives of Pt(II) are rare, consistent with the reluctance of Pt(II) to become pentacoordinate.

Alkyl and aryl platinum(II) complexes are often prepared by oxidative addition of an alkyl halide or aryl halide to a Pt(0) precursor such as tetrakis(triphenylphosphine)platinum(0) or Pt(C₂H₄)(PPh₃)₂. Alternatively, platinum(II) chlorides are susceptible to alkylation:^[4]^[5]

PtCl₂(SMe₂)₂ + 2 MeLi → PtMe₂(SMe₂)₂ + 2 LiCl

The dimethylsulfide ligands in PtMe₂(SMe₂)₂ can be displaced by other ligands.

Many organoplatinum(II) complexes arise via ortho-metalation and related intramolecular C-H activation processes.

Organoplatinum(IV)

The first organoplatinum compound ever synthesised was trimethylplatinum iodide from platinum(IV) chloride and methylmagnesium iodide, reported by Pope and Peachey in 1907.^[6]^[7] The compound adopts a cubane-like structure with four triply bridging iodide ligands. "Tetramethylplatinum" was claimed in 1952 by Henry Gilman as a derivative of this tetramer, but this claim was later shown to be incorrect ("Tetramethylplatinum" proved to be [PtMe₃OH]₄). Salts of [PtMe₆]²⁻ and [PtMe₄]²⁻ have been characterized.^[8]

Organoplatinum(IV) hydrides are rare.^[9] The first isolated representatives were prepared from organotin halides or acids with orthometalated arylplatinum(II) compounds. The compound Me(PEt₃)₂PtOTf reacts reversibly with triflic acid between -60 and -80 °C, forming methane and (PEt₃)₂Pt(OTf)₂ at -20 °C. Weak acids often suffice even water and alcohol and in C-H bond activation the proton source is an alkane.

Catalysis

Heterogeneous catalysts based on platinum play a major role in the petrochemical industry, and it is assumed that these useful reactions proceed via surface-bound organoplatinum intermediates. Better defined but less commercially significant are homogeneous catalysts based on platinum.

For hydrosilylation, H₂PtCl₆ ("Speier's catalyst") is an important catalyst. Mechanisms for this catalytic system usually assume intermediates that contain hydride, silyl ligand (R₃Si), and alkene ligands.^[10] Cis-dichlorobis(diethyl sulfide)platinum(II) and Karstedt’s catalyst (adduct of divinyltetramethyldisiloxane and chloroplatinic acid) also catalyse hydrosilylation.^[11] Many metallodendrimers have repeating units based on organoplatinum compounds.

Idealized mechanism for metal-catalysed hydrosilylation of an alkene.

Research themes

Organoplatinum compounds are implicated in the Shilov system for the conversion of methane into methyl chloride. Strenuous efforts have been made, thus far unsuccessfully, to extend this reactivity to practical methods for functionalizing methane.^[12]

Platinum compounds are also found to be catalysts in enyne cycloisomerisation.^[13]

References

^ Nickel, Palladium and Platinum (Comprehensive Organometallic Chemistry II) R.J. Puddephatt (Editor) 2002 0080423167
^ Synthesis of Organometallic Compounds: A Practical Guide Sanshiro Komiya Ed. S. Komiya, M. Hurano 1997
^ Jwu-Ting Chen "Platinum: Organometallic Chemistry" in Encyclopedia of Inorganic Chemistry 2006, John Wiley & Sons, New York. doi:10.1002/0470862106.ia195
^ Costa, E.; Pringle, P. G.; Ravetz, M. (1997). "[(1,2,5,6-N)-1,5-Cyclooctadiene]Dimethyl-Platinum(II)". Inorganic Syntheses. 31: 284. doi:10.1002/9780470132623.ch49.
^ Hill, Geoffrey S.; Irwin, Michael J.; Levy, Christopher J.; Rendina, Louis M.; Puddephatt, Richard J. (1998). "Platinum(II) Complexes of Dimethyl Sulfide". Inorganic Syntheses. 32: 149. doi:10.1002/9780470132630.ch25.
^ "Proceedings of the Chemical Society, Vol. 23, No. 323". Proceedings of the Chemical Society (London). 23 (323): 81–94. 1907. doi:10.1039/PL9072300081.
^ Pope, W. J.; Peachey, S. J. (1909). "LXXIII.?The alkyl compounds of platinum". Journal of the Chemical Society, Transactions. 95: 571. doi:10.1039/CT9099500571.
^ Greenwood, N. N.; & Earnshaw, A. (1997). Chemistry of the Elements (2nd Edn.), Oxford: Butterworth-Heinemann. ISBN 0-7506-3365-4.
^ Puddephatt, R. (2001). "Platinum(IV) hydride chemistry". Coordination Chemistry Reviews. 219-221: 157–185. doi:10.1016/S0010-8545(01)00325-3.
^ C. Elschenbroich, Organometallics (2006) Wiley and Sons-VCH: Weinheim. ISBN 978-3-527-29390-2
^ Kettler, P. B. (2003). "Platinum Group Metals in Catalysis: Fabrication of Catalysts and Catalyst Precursors". Organic Process Research & Development. 7 (3): 342–354. doi:10.1021/op034017o.
^ Stahl, Shannon S.; Labinger, Jay A.; Bercaw, John E. (1998). "Homogeneous Oxidation of Alkanes by Electrophilic Late Transition Metals". Angewandte Chemie International Edition. 37: 2180–2192. doi:10.1002/(SICI)1521-3773(19980904)37:16<2180::AID-ANIE2180>3.0.CO;2-A.
^ Zhang, L.; Sun, J.; Kozmin, S. ��A. (2006). "Gold and Platinum Catalysis of Enyne Cycloisomerization". Advanced Synthesis & Catalysis. 348 (16–17): 2271. doi:10.1002/adsc.200600368. replacement character in |first3= at position 4 (help)

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Japanese Journal

Synthesis and Reactions of Organoplatinum Compounds of C60, C60Ptn.

Nagashima Hideo,Kato Yoshiyuki,Yamaguchi Hirofumi,Kimura Eiji,Kawanishi Teruhiko,Kato Masanao,Saito Yahachi,Haga Masaaki,Itoh Kenji
Chemistry Letters (7), 1207-1210, 1994
… The organoplatinum compound of C60, C60Ptn …
NAID 130004419529

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リンク元	「有機白金化合物」
関連記事	「compound」

「有機白金化合物」

　　[★]

英: organoplatinum compound

「compound」

　　[★]

化合物、配合、複方の、配合する

関: combination、compositus、mixture

[1] Nickel, Palladium and Platinum (Comprehensive Organometallic Chemistry II) R.J. Puddephatt (Editor) 2002 0080423167

[2] Synthesis of Organometallic Compounds: A Practical Guide Sanshiro Komiya Ed. S. Komiya, M. Hurano 1997

[3] Jwu-Ting Chen "Platinum: Organometallic Chemistry" in Encyclopedia of Inorganic Chemistry 2006, John Wiley & Sons, New York. doi:10.1002/0470862106.ia195

[4] Costa, E.; Pringle, P. G.; Ravetz, M. (1997). "[(1,2,5,6-N)-1,5-Cyclooctadiene]Dimethyl-Platinum(II)". Inorganic Syntheses. 31: 284. doi:10.1002/9780470132623.ch49.

[5] Hill, Geoffrey S.; Irwin, Michael J.; Levy, Christopher J.; Rendina, Louis M.; Puddephatt, Richard J. (1998). "Platinum(II) Complexes of Dimethyl Sulfide". Inorganic Syntheses. 32: 149. doi:10.1002/9780470132630.ch25.

[6] "Proceedings of the Chemical Society, Vol. 23, No. 323". Proceedings of the Chemical Society (London). 23 (323): 81–94. 1907. doi:10.1039/PL9072300081.

[7] Pope, W. J.; Peachey, S. J. (1909). "LXXIII.?The alkyl compounds of platinum". Journal of the Chemical Society, Transactions. 95: 571. doi:10.1039/CT9099500571.

[8] Greenwood, N. N.; & Earnshaw, A. (1997). Chemistry of the Elements (2nd Edn.), Oxford: Butterworth-Heinemann. ISBN 0-7506-3365-4.

[9] Puddephatt, R. (2001). "Platinum(IV) hydride chemistry". Coordination Chemistry Reviews. 219-221: 157–185. doi:10.1016/S0010-8545(01)00325-3.

[10] C. Elschenbroich, Organometallics (2006) Wiley and Sons-VCH: Weinheim. ISBN 978-3-527-29390-2

[11] Kettler, P. B. (2003). "Platinum Group Metals in Catalysis: Fabrication of Catalysts and Catalyst Precursors". Organic Process Research & Development. 7 (3): 342–354. doi:10.1021/op034017o.

[12] Stahl, Shannon S.; Labinger, Jay A.; Bercaw, John E. (1998). "Homogeneous Oxidation of Alkanes by Electrophilic Late Transition Metals". Angewandte Chemie International Edition. 37: 2180–2192. doi:10.1002/(SICI)1521-3773(19980904)37:16<2180::AID-ANIE2180>3.0.CO;2-A.

[13] Zhang, L.; Sun, J.; Kozmin, S. ��A. (2006). "Gold and Platinum Catalysis of Enyne Cycloisomerization". Advanced Synthesis & Catalysis. 348 (16–17): 2271. doi:10.1002/adsc.200600368. replacement character in |first3= at position 4 (help)

CH																	He
CLi	CBe											CB	CC	CN	CO	CF	Ne
CNa	CMg											CAl	CSi	CP	CS	CCl	CAr
CK	CCa	CSc	CTi	CV	CCr	CMn	CFe	CCo	CNi	CCu	CZn	CGa	CGe	CAs	CSe	CBr	CKr
CRb	CSr	CY	CZr	CNb	CMo	CTc	CRu	CRh	CPd	CAg	CCd	CIn	CSn	CSb	CTe	CI	CXe
CCs	CBa		CHf	CTa	CW	CRe	COs	CIr	CPt	CAu	CHg	CTl	CPb	CBi	CPo	CAt	Rn
Fr	CRa		Rf	Db	CSg	Bh	Hs	Mt	Ds	Rg	Cn	Uut	Fl	Uup	Lv	Uus	Uuo
		↓
		CLa	CCe	CPr	CNd	CPm	CSm	CEu	CGd	CTb	CDy	CHo	CEr	CTm	CYb	CLu
		Ac	CTh	CPa	CU	CNp	CPu	CAm	CCm	CBk	CCf	CEs	Fm	Md	No	Lr

Core organic chemistry	Many uses in chemistry
Academic research, but no widespread use	Bond unknown

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organoplatinum compound