Synthetic, Structural, and Theoretical Studies on a Novel Rhodium(I) Complex Containing a π-Allyl-Type Ylide Ligand

Helmut Werner; Norbert Mahr; Gernot Frenking; Volker Jonas

doi:10.1021/om00002a008

Synthetic, Structural, and Theoretical Studies on a Novel Rhodium(I) Complex Containing a π-Allyl-Type Ylide Ligand

Helmut Werner, Norbert Mahr, Gernot Frenking, Volker Jonas

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Abstract

Whereas the reaction of [RhCl(P-i-Pr₃)₂]_n (1) with [CPh(Me)OH](CO₂Et)CN₂ and PhCHN₂ gives the diazoalkane and dinitrogen complexes trans-[RhCl{N₂C(CO₂Et)(CPh(Me)OH)}(P-i-Pr₃)₂] (2) and trans-[RhCkl(N₂)(P-i-Pr₃)₂] (3), respectively, the mononuclear yliderhodium(I) compound [RhCl(P-i-Pr₃)(i-Pr₃P=CHC(O)Ph)] (4) is obtained on treatment of 1 with PhC-(═O)CHN₂. It reacts with CO or CN-t-Bu to generate the formerly unknown acyl ylide i-Pr₃-PCHC(O)Ph (5). The X-ray structure analysis of 4 (monoclinic, space group P2₁/c (No. 14), with a = 11.280(3) Å, b = 15.201(2) Å, c = 17.041(5) Å, β= 92.36(1)°, and Z = 4) reveals the presence of a η^³-allly-type unit which is coordinated via oxygen and two carbon atoms to the metal center. The nature of the bonding between the modified acyl ylide ligand H₃PCHC-(=O)CH₃ and rhodium(I) has been investigated by ab initio methods at the MP2 level. The calculated structure of the hypothetical molecule [RhCl(PH₃){H₃PCHC(O)CH₃}] (4') is very similar to the geometry of 4 obtained by X-ray analysis. In contrast to 1, the alkynylrhodium-(I) compounds trans-[Rh(C≡CR)(C₂H₄)(P-i-Pr₃)₂] (6, 7) react with PhC(═O)CHN₂ to give the diazoalkane complexes trans-[Rh(C≡CR){N₂C(H)(COPh)}(P-i-Pr₃)₂] (11,15). The preparation of other derivatives of composition trans-[Rh(C≡CR)(N₂CR“R”)(P-i-Pr₃)₂] (8-10,12-14) will also be described.

Original language	English
Pages (from-to)	619-625
Number of pages	7
Journal	Organometallics
Volume	14
Issue number	2
DOIs	https://doi.org/10.1021/om00002a008
State	Published - Feb 1995
Externally published	Yes

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@article{881295ff655f43198d285cb0617ecbd6,

title = "Synthetic, Structural, and Theoretical Studies on a Novel Rhodium(I) Complex Containing a π-Allyl-Type Ylide Ligand",

abstract = "Whereas the reaction of [RhCl(P-i-Pr3)2]n (1) with [CPh(Me)OH](CO2Et)CN2 and PhCHN2 gives the diazoalkane and dinitrogen complexes trans-[RhCl{N2C(CO2Et)(CPh(Me)OH)}(P-i-Pr3)2] (2) and trans-[RhCkl(N2)(P-i-Pr3)2] (3), respectively, the mononuclear yliderhodium(I) compound [RhCl(P-i-Pr3)(i-Pr3P=CHC(O)Ph)] (4) is obtained on treatment of 1 with PhC-(═O)CHN2. It reacts with CO or CN-t-Bu to generate the formerly unknown acyl ylide i-Pr3-PCHC(O)Ph (5). The X-ray structure analysis of 4 (monoclinic, space group P21/c (No. 14), with a = 11.280(3) {\AA}, b = 15.201(2) {\AA}, c = 17.041(5) {\AA}, β= 92.36(1)°, and Z = 4) reveals the presence of a η3-allly-type unit which is coordinated via oxygen and two carbon atoms to the metal center. The nature of the bonding between the modified acyl ylide ligand H3PCHC-(=O)CH3 and rhodium(I) has been investigated by ab initio methods at the MP2 level. The calculated structure of the hypothetical molecule [RhCl(PH3){H3PCHC(O)CH3}] (4') is very similar to the geometry of 4 obtained by X-ray analysis. In contrast to 1, the alkynylrhodium-(I) compounds trans-[Rh(C≡CR)(C2H4)(P-i-Pr3)2] (6, 7) react with PhC(═O)CHN2 to give the diazoalkane complexes trans-[Rh(C≡CR){N2C(H)(COPh)}(P-i-Pr3)2] (11,15). The preparation of other derivatives of composition trans-[Rh(C≡CR)(N2CR“R”)(P-i-Pr3)2] (8-10,12-14) will also be described.",

author = "Helmut Werner and Norbert Mahr and Gernot Frenking and Volker Jonas",

year = "1995",

month = feb,

doi = "10.1021/om00002a008",

language = "英语",

volume = "14",

pages = "619--625",

journal = "Organometallics",

issn = "0276-7333",

publisher = "American Chemical Society",

number = "2",

}

TY - JOUR

T1 - Synthetic, Structural, and Theoretical Studies on a Novel Rhodium(I) Complex Containing a π-Allyl-Type Ylide Ligand

AU - Werner, Helmut

AU - Mahr, Norbert

AU - Frenking, Gernot

AU - Jonas, Volker

PY - 1995/2

Y1 - 1995/2

N2 - Whereas the reaction of [RhCl(P-i-Pr3)2]n (1) with [CPh(Me)OH](CO2Et)CN2 and PhCHN2 gives the diazoalkane and dinitrogen complexes trans-[RhCl{N2C(CO2Et)(CPh(Me)OH)}(P-i-Pr3)2] (2) and trans-[RhCkl(N2)(P-i-Pr3)2] (3), respectively, the mononuclear yliderhodium(I) compound [RhCl(P-i-Pr3)(i-Pr3P=CHC(O)Ph)] (4) is obtained on treatment of 1 with PhC-(═O)CHN2. It reacts with CO or CN-t-Bu to generate the formerly unknown acyl ylide i-Pr3-PCHC(O)Ph (5). The X-ray structure analysis of 4 (monoclinic, space group P21/c (No. 14), with a = 11.280(3) Å, b = 15.201(2) Å, c = 17.041(5) Å, β= 92.36(1)°, and Z = 4) reveals the presence of a η3-allly-type unit which is coordinated via oxygen and two carbon atoms to the metal center. The nature of the bonding between the modified acyl ylide ligand H3PCHC-(=O)CH3 and rhodium(I) has been investigated by ab initio methods at the MP2 level. The calculated structure of the hypothetical molecule [RhCl(PH3){H3PCHC(O)CH3}] (4') is very similar to the geometry of 4 obtained by X-ray analysis. In contrast to 1, the alkynylrhodium-(I) compounds trans-[Rh(C≡CR)(C2H4)(P-i-Pr3)2] (6, 7) react with PhC(═O)CHN2 to give the diazoalkane complexes trans-[Rh(C≡CR){N2C(H)(COPh)}(P-i-Pr3)2] (11,15). The preparation of other derivatives of composition trans-[Rh(C≡CR)(N2CR“R”)(P-i-Pr3)2] (8-10,12-14) will also be described.

AB - Whereas the reaction of [RhCl(P-i-Pr3)2]n (1) with [CPh(Me)OH](CO2Et)CN2 and PhCHN2 gives the diazoalkane and dinitrogen complexes trans-[RhCl{N2C(CO2Et)(CPh(Me)OH)}(P-i-Pr3)2] (2) and trans-[RhCkl(N2)(P-i-Pr3)2] (3), respectively, the mononuclear yliderhodium(I) compound [RhCl(P-i-Pr3)(i-Pr3P=CHC(O)Ph)] (4) is obtained on treatment of 1 with PhC-(═O)CHN2. It reacts with CO or CN-t-Bu to generate the formerly unknown acyl ylide i-Pr3-PCHC(O)Ph (5). The X-ray structure analysis of 4 (monoclinic, space group P21/c (No. 14), with a = 11.280(3) Å, b = 15.201(2) Å, c = 17.041(5) Å, β= 92.36(1)°, and Z = 4) reveals the presence of a η3-allly-type unit which is coordinated via oxygen and two carbon atoms to the metal center. The nature of the bonding between the modified acyl ylide ligand H3PCHC-(=O)CH3 and rhodium(I) has been investigated by ab initio methods at the MP2 level. The calculated structure of the hypothetical molecule [RhCl(PH3){H3PCHC(O)CH3}] (4') is very similar to the geometry of 4 obtained by X-ray analysis. In contrast to 1, the alkynylrhodium-(I) compounds trans-[Rh(C≡CR)(C2H4)(P-i-Pr3)2] (6, 7) react with PhC(═O)CHN2 to give the diazoalkane complexes trans-[Rh(C≡CR){N2C(H)(COPh)}(P-i-Pr3)2] (11,15). The preparation of other derivatives of composition trans-[Rh(C≡CR)(N2CR“R”)(P-i-Pr3)2] (8-10,12-14) will also be described.

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U2 - 10.1021/om00002a008

DO - 10.1021/om00002a008

M3 - 文章

AN - SCOPUS:0000153411

SN - 0276-7333

VL - 14

SP - 619

EP - 625

JO - Organometallics

JF - Organometallics

IS - 2

ER -

Synthetic, Structural, and Theoretical Studies on a Novel Rhodium(I) Complex Containing a π-Allyl-Type Ylide Ligand

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