Assign the anonymous object as you would any other value.
people["4"] = { name: 'John' };
For what it's worth, since your keys are numeric, you can also use indexes with a zero index and make people an array.
var people = [ { name: 'Joe' },
{ name: 'Sam' },
{ name: 'Eve' } ];
and
alert( people[2].name );
people[3] = { name: 'John' };
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