Intramolecular C-H bond activation promoted by the d[sup 0] [([eta][sup 5]-C[sub 5]Me[sub 5])W([double bond]NR)[sub 2]][sup +] functional group

Journal Article · Thu Dec 31 23:00:00 EST 1992 · Organometallics; (United States)

DOI:https://doi.org/10.1021/om00025a019· OSTI ID:6567473

Huber, S R; Baldwin, T C; Wigley, D E ^[1]

---

1. Univ. of Arizona, Tucson (United States)

The bis(imido) complex of tungsten, W([double bond]NAr)[sub 2]Cl[sub 2](THF)[sub 2] (Ar = 2,6-C[sub 6]H[sub 3][sup i]Pr[sub 2]) reacts with Li[C[sub 5]Me[sub 5]] to provide burgundy ([eta][sup 5]-C[sub 5]Me[sub 5])W([double bond]NAr)[sub 2]Cl (1) in high yield. Compound 1 may be functionalized using MeLi, PhLi, or LiBEt[sub 3]H[sub *] (H[sup *] = H or D) to provide ([eta][sup 5]-C[sub 5]Me[sub 5])W([double bond]NAr)[sub 2]Me (2), ([eta][sup 5]-C[sub 5]Me[sub 5])W([double bond]NAr)[sub 2]Ph (3), ([eta][sup 5]-C[sub 5]Me[sub 5])W([double bond]NAr)[sub 2]H (4), and ([eta][sup 5]-C[sub 5]Me[sub 5])W([double bond]NAr)[sub 2]D (4-d) in moderate to high yields. ([eta][sup 5]-C[sub 5]Me[sub 5])W([double bond]NAr)[sub 2]Cl (1) crystallizes in the monoclinic P2[sub 1]/n (no. 14) [Angstrom][sup 3] with Z = 4 and [rho][sub calcd] = 1.46 g cm[sup [minus]3]. The molecular structure of 1 is characterized by nearly identical imido ligands with W-N-C[sub ipso] angles averaging 169.3 (4)[degrees] and W-N bonds averaging 1.783 (4) [Angstrom]. Upon reaction of ([eta][sup 5]-C[sub 5]Me[sub 5])W([double bond]NAr)[sub 2]Cl (1) with LiNHAr, the tucked-in complex ([eta][sup 5],[eta][sup 1]-C[sub 5]Me[sub 4]CH[sub 2])W([double bond]NAr)[sub 2] (5) is formed in nearly quantitative yield. Experiments are presented which indicate the most likely mechanism of formation of 5 involves the intermediacy of the substituted complex, ([eta][sup 5]-C[sub 5]Me[sub 5])W([double bond]NAr)[sub 2](NHAr). 48 refs., 1 fig., 3 tabs.

• OSTI ID: 6567473
• Journal Information: Organometallics; (United States), Journal Name: Organometallics; (United States) Vol. 12:1; ISSN ORGND7; ISSN 0276-7333
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
ALKYLATED AROMATICS
AROMATICS
CHEMICAL ACTIVATION
CHEMICAL REACTION YIELD
CHEMICAL REACTIONS
CRYSTAL LATTICES
CRYSTAL STRUCTURE
DEUTERIUM COMPOUNDS
HYDROGEN COMPOUNDS
LIGANDS
MOLECULAR STRUCTURE
MONOCLINIC LATTICES
ORGANIC COMPOUNDS
ORGANOMETALLIC COMPOUNDS
REFRACTORY METAL COMPOUNDS
TRANSITION ELEMENT COMPOUNDS
TUNGSTEN COMPOUNDS
YIELDS